-------
             TABLE  23.  INORGANIC  TRACE ELEMENT  COMPOSITIONS IN  INCINERATOR SAMPLES
Sample Test.
Feed sludge 2
3
4
Ave
Boltom at,h 2
j
4
Ave
Mechanical hopper 2
ash 3
4
Ave
Baghouse dust 2
3
4
Ave
AS
6.8
3.5
8.1
6.1
0.35
40,5
73
33
0.02
6.5
0.88
0.5
0.53
11.4
«
20
Be
0.001
<9 x 10-4
<9 x 10-4
NO
1.0
0.7
1.0
0.9
2.0
0.9
0.9
1.3
0.4
0.4
0.2
0.3
Cd
<0.02
<0.02
<0.02
ND
• <0.02
<0.02
<0.02
ND
0.1
<0.02
<0.02
0.03
0.3
0.4
0.1
0.3
In
10.0
7.0
3.0
6.6
2.0
5.0
8.0
5.0
90
40
30
53
750
750
SOO
700
Cr
2.7
2.6
2.0
2.5
1.0
0.6
1.1
0.9 .
1.9
2.0
1.8
1.9
2.9
4.4
3.4
3.5
Cu
36
48
19
34
29
57
29
. 33
85
120
70
92
230
305
2?5
253
Pb
<1
<1
<1
NO
<1
<1
<1
NO
100
10
10
40
1500
1500
WOO
1400
Nt
<0.2
<0.2
<0.2
NO
0.6
0.5
0.4
0.5
0.3
0.3
0.2
0.3
0.4
0.4
<0.2
0.3
Ag
<0.06
<0.06
<0.06
NO
<0.06
<0.06
<0.06
NO
<0.06
<0.06
<0.06
ND
0.1
0.1
0.1
0.1
Sb
<0.05
0.25
0.16
0.13
<5.0
<5.0
<5.0
ND
<5.0
<5.0
<5.0
ND
25
38
28
30
Hg
0.01
0.01
0.02
0.013
1.0
2.0
0.9
1.3
3.0
4.0
2.0
3.0
5
12
11
9
Se
<0.05
0.05
0.10
0.05
<5.0
10.0
10.0
10.0
<5.0
<5.0
<5.0
HD
10
10
10
10
Tl
<0.001
-------
e_n
                             TABLE 24.   RATES OF  DISCHARGE AND  EFFICIENCY  OF DESTRUCTION
                                          FOR  NAPHTHALENE  AND PHENOL

Test 2



Test 3



Test 4





Naphthalene
Phenol
Solid rate

Naphthalene
Phenol
Sol;d rate

Naphthalene
Phenol
Sol id rate
Feed
(g/sec)

0.10
0.10
79

0.08
0.08
79

0.05
0.11
79
Bottom ash
(g/sec)

<5 x
<5 x
<5

<9 >
<4 x
<5

<4.8
<3 x
<5

io-5
10-7


io-5
10-6


x 10-5
IO'6

Mech. hop.
(g/sec)

a x lo-J
<\ x IO-6
<10

<1.7 x IO-4
<1 x ID'6
<10

<2.2 x IO-5
<1 x ID"6
<10
Baghouse
(g/sec)

<5 x ID'5 „
<2.5 x 10-9
<5

<1.9 x 1Q~6
<1 x 10'6
<5

<2.5 x 10"5
<1.5 x 1Q-6
<5
Gas
(g/sec)

3.9 x IO--1
2.9 x 10~5
(6.85)*

1 x IO-3
a. 9 x io-5
(6.65)*

1.1 x IO-3
1.6 r IO-5
(7.0)*
Total out
(g/sec)

3.9 x IO-3
2.9 x lO'5


1 x IO-3
<2 x IO-5


1.1 x ID"3
1.6 x IO-5

Efficiency
(percent)

96.1
99.97


98.7
>99.99


97.8
99.99

           Assumptions:  Feed rate, all cases = 79 g/sec sludge; ash quantity is  5  g/sec total, but  some unburned
en                     organics were observed in the mechanical hopper  thus <10g  it used.

          *Sm3/sec (23°C and 1 atm)
-------
indestructable material as tracers.  Upon observation of data in Table 23, it
is apparent that the partition of various metals into each ash component
(bottom, hopper, baghouse) is dependent on the species, not the ash collecting
component.  In addition the large amount of metal component contributed by
either the wood or sludge added a compounding complication to tracer analysis.

       Only two organic compounds were detected  in the stack emissions.  The
mass balance and destruction efficiency for these compounds were developed as
follows:

       •   Measured rates were available for the feed and stack gas
           emissions.  The feed rate was 72 I/sec with a density of 1.1 g/ml
           or 79 (range 66 to 99) g/sec.  The gas volume ranged from 6.85 to
           6.99 sm3/sec (23°C and 1 ata).  The exhaust gas particulate
           material was below detectable levels  (<10~3 g/sm^ or <10~^
           g/sec), so solids in the gas stream were negligible.

       e   Rates for the three ash streams were not directly measurable;
           alternately the effect on mass balances was determined for maximum
           values based on the total ash generated.  Total ash was calculated
           from the feed wood and sludge added.  Ash composes 0.30 percent of
           Douglas-fir wood and 0.55 percent of Douglas-fir bark.   Wood
           without bark was fed during the boiler test sequence.  Based on
           1,550 g/sec of wet wood and 79 g/sec sludge, the ash was calculated
           to be 5 g/sec.  The mechanical hopper was observea to contain some
           unburned char thus a higher total quantity was assumed
           conservatively at lOg.  Since the phenol and naphthalene losses
           that could occur through these ash amounts were too small to affect
           the destruction efficiency, their calculation provided an
           informative maximum.

       Using these calculated rates, the mass flowrates of naphthalene and
phenol (the only observed organic emissions) were derived and are presented in
Table 24.  The destruction efficiency also is presented, as calculated from
the equation:


                            Rf Cf,j -     R> C
                        E =                        x 100


where

       Rf = feed rate of sludge
      Cf-j = concentration of jtncomponent in the feed
       R-j = rate of discharge of itn stream
      C] •; = concentration of jt" component in i'-'1 stream

       Percent destruction of the two organic components of the sludge range
from 96+  to >99.99 percent.  These rates are the 1owest values for any of the
16 organic constituents analyzed for in the stacK gas.  In fact, with the
exception of naphthalene, all components were destroyed to 99.99 percent
                                       57
-------
completion.  The high stack value of naphthalene  appears an oddity considering
other component similarity  in feed concentration  and  time-temperature
requirements for destruction.  Naphthalene contamination in other sample
containers (discarded)  is documented in Appendix  C.

       Table 25 compares the content of the raw creosote, the working penta
solution, the sludge wastewater, and the fuel  (sludge and wood chips) for
represftntati 'e compounds.  Although incineration  fuel is similar in relative
proportion to the starting preservative solutions, the variations in relative
quantities cf compounds  in sludge and penta are indicative of too few samples
to provide precise values.  The major changes  through fie process are
dilution, first with watjr and then with wood  chips.

       As shown in the  data tables, the ash samples contained ppm quantities
of polynuclear aromatics.  Whether these arise from unburned fuel or by
partial combustion is not known.  The absence  of  phenols in the bottom ash is
evidence in favor of the latter hypothesis.  Only ne.phthalene nnd low levels
of phenols were detected in the XAD-2 cartridge samples; naphthalene was
consistently detected.   For further information see chromatograrns in
Appendix C.

       To summarize, the incineration process  gives rise to very low or
undetectable levels of  airborne volatile pollutants.  The bottom ash from this
process uoes contain significant concentrations of uncombusted material.

       Section 8 discusses analysis of plant C samples for chlorinated dioxins
and furans.

              TABLE 25.  SELECTED COMPONENTS IN WOOD PRESERVATIVE
                         SOLUTIONS AND INCINERATION FUEL
                                       Concentration ng/g

    Compound
                       Creosote         Penta           Sludge          Fuel
Phenol
Naphthalene
Penta
Phenanthrene
Toluene
8,000
1,700
1,700
37,000
1,401'
4.00U
660
16,000
1,200
NA
1,200
900
250
850
8
12
18
. 15
18
NA
                                       58
-------
                                   SECTION 8

       CHARACTERIZATION OF CHLORODIBENZOFURANS AND CHLORODIBENZODIOXINS
           DISCHARGED FROM A BOILER CO-FIRING WOOD PRESERVING WASTES
       The existence of dioxins and furans in combustion ash and wood
preserving waste is well documented(2,6).   Thus, as an effort to quantify
the amount of these compounds in emissions or residues from the co-firing of
wood and preserving waste sludge, analyses of the wastes, exhaust gas and
three ash components was accomplished.  Results of these analyses with input
from three different laboratories are presented in this section along with a
brief discussion of procedures used.

8.1    FURAN AND DIOXIN ANALYSIS OF STACK GAS, WASTE,  AND ASH

       Samples utilized in the chlorodibenzofuran (CDF) and
chlorodibenzodioxin (CDD) analysis were the samples identified in Section 7.
Abbreviations for various chlorinated homologs are listed in Table 26 along
with the possible number of isomers of each.  The analytical results of CDF
and CDD are presented in Tables 27 to 32.

       No CDFs or CDDs were detected in the air emissions.   The detection
limits were <10 ug/m^ (lo ppt w/v).

       Both CDFs and CDDs were found in the treating penta  solution, waste
sludge and the ash.  Although these materials were defected, the quantity
measured was not consistent and depended or. the analyzing laboratory's
procedures.

       Ash sludge and penta in oil samples were analyzed by multiple
laboratories using split samples.  Tables 27 to 29 report values for Lab A
while Table 32 reports resuUs for Labs A, B and C.  To better understand the
values presented, ths, sample preparation procedures are compared in Table 33.
Also it should be seated that the recovery reported by the  three labs is quite
different, varying between less than 40 percent and over 130 percent.  Spike
and recovery data for Labs A and B are given in Appendix C.   Recovery for
Lab C was reported as 50 to 80 percent but not documented during analysis.

       For each of the listed homologs of  CCD and CDF, typically only a single
isomer was available for calibration.   The total number of  isomers was deduced
by comparing the (JC/MS properties of the standard to those  unknown compounds
exhibiting similar properties.  However, since not all isomers of a given
group were available for calibrating retention times,  a given mass
                                       59
-------
TABLE 26.  SUMMARY OF  ABBREVIATIONS FC.i CHLORODIBENZOHJRAN
           AND CHLORODIBflNZOLJlOXlNS
Abbrevi ations
MCDF
DCDF
TrCOf
TCDF
PCDF
HxCDF
HpCDF
OCDF
MCDD
DCDD
TrCDD
TCDD
PCDD
HxCOD
HpCDD
OCDD
Name
Monochlorodiben?cfuran
Dichlorodibenzofuran
Trichlorodibenzofuran
Tetrachlorodibenzofuran
Pentachlorodibenzofuran
Hexachlorodibenzof uran
Heptachlorodibenzofuran
Octachlorodihenzofuran
Monochlorodibenzodioxin
Dichlorodibenzodioxin
Trichlorodibenzodioxin
Tetrachlorod'ibenzodioxin
Pentachlorodibenzodioxin
Hexachlorodibenzodioxin
Heptachlorodibenzodioxin
Octachlorodibenzodioxin
Possible isomers
i\
16
28
38
28
16
4
1
2
10
14
c'2
in
10
2
1
                            60
-------
    TABLE 27.  CHLORODIBENZOFURAN  AND CHLORODIBENZOOJOXIN ANALYTICAL RESULTS
               FOR TREATMENT OIL  (4.5 PERCENT  PENTA IN OIL)  — LABS A AND B
Monomer
of COD
or COF*
MCDF
DCDF
TrCDF
TCDF
PCDF
HxCDF
HpCDF
OCDF
MCOD
DCDD
TrCDD
TCDD
PCDD
HxCDO
Hp-CDD
OCDD
Total
number of
apparent isomers**
4
2
4
5
5
5
2
1
2
2
2
NR
6
4
2
1
Total detected***
(ng/g)
2 (180)+
2 (1800)
10 (ND)
18 (ND)
140 (920)
1800 (2700)
114 (3100)
710 (4660)
1.5 (i)
2 (i)
3.5 (i)
1.1 (i)
33 (i)
570 (1,540)
260 (17,100)
4000 (>17,000)
Minimum
detectable
concentration
(ng/g)
0.4
0.8
1.2
0.1
1
1
1
3
0.4
0.8
1.2
0.5
0.3
1
1
3
  *See table 8-1 for summary of norr>encl ature
 **See text
   •J \f ^- V t_ /\ U
***Not corrected for recover}', these  concentrations  represent minimum values
  +Analysis reported by Lab B for monomer  groups  only isomers and detection
  • 1 T m i +• i-iri-f- ."iTwnn
  •.limit not given
  ^Interferences too large to quantify
  \
                                       61
-------
    TABLE  28.   CHLORODIBENZOFURAN AND CHLORIDIBENZODIOXIN ANALYTICAL  RESULTS
               FOR  DAY  2  COMPOSITE SLUDGE  LIQUID — LAB A
    CDD/CDF^
                                        Minimum
                                       detectable
   Total  no.  of     Total  detected*** concentration
apparent  isomers**        (ng/g)
MCDF
DCDF
TrCDF
TCDF
PCDF
HxCDF
MCDD
DCOD
TrCDD
TCDD
PCDD
HxCDD
4
0
0
0
1
2
1
0
0
0
3
4
0.6
0
0
0
0.3
0.8
0.2
0
0
0
0.6
2.5
0.2
0.3
0.7
0.1
0.2
0.5
0.2
0.3
0.7
0.9
0.3
0.5
  *See Table  7-6  for summary of nomenclature
 **See text
***Not corrected  for recovery,  these concentrations represent minimum values;
   all s,ludge is  wet weight
                                       62
-------
    TABLE  29.   CHLORQDIEENZOFURAN AliD CHLORODIBENZODIOXIN ANALYTICAL RESULTS
               FOR DAY 4 COMPOSITE SLUDGE LIQUID — LAB A
CDD/COF*
MCDF
DCDF
TrCDF
TCDF
PCDF
HxCDF
HpCDF
OCDF
MCDO
DCDD
TrCDD
TCDD
PCDD
HxCDD
HpCDD
OCDD
Total no. of
apparent isomers**
3
0
0
0
1
3
2
1
1
1
0
0
0
3
2
1
Total detected***
(ng/y)
0.7
0
0
0
0.5
8
7
2
0.6
0.4
0
0
0
10
70
230
Minimum
detectable
concentration
(ng/g)
0.2
0.4
0.9
0.05
0.2
2
1
1
0.2
0.4
0.9
0.9
1
1
1
1
  *See  Table  7-6 for suTimary of nomenclature
 **See  text
***Results  corrected for recovery
                                       63
-------
    TABLE  30.   CHLORODIBENZOFURAN AND CHLORODIBENZODFOXIN ANAIYTICAL RESULTS
               FOR DAY 3 COMPOSITE ASM — LAB A
    CDD/CDF*
                                        Minimi."
                                       detectable
   Total no. of     Total detected*** concentration
apoarent isomers**       (ng/g)          (ng/g)
NCDF
DCDF
TrCDF
TCDF
PCDF
HxCOF
HpCOF
OCDF
MCDD
DCDO
TrCDD
TCOD
PCDD
HxCDO
HpCOO
OCDD
3
8
6
8
5
2
2
1
1
5
5
NR
5
1
2
1
90
7.5
20
1.2
0.7
1
1.6
1.2
2
1
5
0.8
2.6
8.7
42
96
0.1
0.3
0.6
0.05
0.1
0.3
0.6
1
0.1
0.3
0.6
0.2
0.1
0.3
1
1
  *See  Table  7-6  for  summary of nomenclature
 **See  text
***Resu1ts corrected  for  recovery
-------
    TABLE  31.   CHLORCDIBENZOFU-AN AND CHLORODIBENZODIOXIN ANALYTICAL RESULTS
               FOR  DAY  4  COM^UVITE ASH —  LAB  A
CDD/CDF*
MCDF
OCDF
TrCDF
TCDF
PCDF
HxCDF
HpCDF
OCDF
MCDD
DCDD
TrCDD
TCDD
PCDD
HxCDD
HpCDD
OCDD
Total no. of
apparent isomers**
3
10
11
8
t;
4
0
0
2
4
4
6
4
3
2
1
Total detected***
(ng/g)
5
8
17
3
3
J.8
0
0
0.7
0.5
6
3.3
6
10
4
1
Minimum
detectable
concentration
(ng/g)
0.1
0.3
0.6
0.1
0.3
0.4
2
1
0.1
0.3
0.6
0.2
0.3
0.4
2
0.8
  *See Table  7-6  for summary of  nomenclature
 **See text
***Results corrected for  recovery
                                       65
-------
        TABLE  32.   CHLORODIBENZOFL'RAN AND CHLORODIBENZODOXIN  ANALYTICAL  RESULTS FOR
                     DAY  2  ASH  — LABS A,  8 AND  C.

MCOF
DCDF
TrCOF
TCDF
PCDF
HjCDF
HpCOF
OCDF
TOTAL CDF
NCDO
DCDS
TrCDO
TCOO
PCDD
K,COD
HpCDO
occo
TOTAL COO
All
3
3
8
7
5
5
2
1

1
4
5
4
5
5
2
1

Compos 1 te4
TD* HDL3
75
25
15
7
8
5
6
2
143
1
5
2
4
32
81
117
200
433
0.1
0.3
0.6
C.5
1.0
1.0
1.0
1.0

O.i
0.3
O.i
0.2
1.0
1.0
1.0
1.0

Lab-8
Bottom Ash CIO Baghouse Ash
AI TO HDL AI TO
«
NR
NR
NR
NR
NR
I*
NR

NR
NR
NR
NR
N.!
NR
W
NR

ND
NO
NO
NO
NO
NO
SO
ND
<420
ND
NO
NO
NO
NO
ND
HO
NO
<800
24
42
45
29
68
115
25
71

102
44
52
47
>.
165
95
198

tv.
NR
NR
NR
NR
NR
NR
NR

NR
NR
NR
NR
NR
NR
NR
NR

29
50
ND
NO
ND
ND
NO
ND
<575
ND
NO
ND
ND
ND
ND
ND
ND
<920
118
KOL
27
48
52
34
77
132
29
163

117
31
60
54
112
189
109
226

Bottom Ash
AI1 TO2
KR5
NP
KR
NR
NR
NR
NR
NR

NR
NR
NR
1
4
3
2
1

NR
NR
NR
 detected (ng/g)
3m]nIITUI^ detertahle 1 mit (ig/q)
?u^po^ i - 'J by *ei.inl  2:5 (bo t torn:
^V\ -- not -tporteJ
-------
                   TABLE 33.  SAMPLE CLEAN-UP PROCEDURES
Prewash

Extraction
  Exchange

  Wash

  Column
                        LAB-A
                              LAS-B
None

Benzene 16 hrs



Hexane

Base, acid
None

Benzen^ 24 hrs



Petroleum ether-

Base, acid
1 Silica base, acid   A^mina
2 Alumina             1:1 CH2C12/HEX
  1:1 CH2C12/HEX
                          LAB-C
IN HC1

Tciuene 36 hrs



Hexane

N.R.

Alumina
1:1 CH2C12/HEX
                                     67
-------
chromatographic peak does not  necessarily  correspond  to  a  single  isomer  of  a
given class;  such peaks may represent  more  than one  isomer.  Hence,  the
authors selected the terminology  "apparent  isomers."

8.2    DISCUSSION OF RESULTS

       Since extraction and cleanup  and  quality assurance  procedures  were
quite different in the three laboratories,  no  detailed comparison or
discussion of results will he  made.   Several general  points  are raised briefly
as follows:

       •   Based on the results given  it is  apparent  the treating solution  of
           pentachlorophenol in oil,  wastewater sludge,  and  resulting ash
           contain chlorinated furans  and  dioxins.  In terms of specific
           monomers TCDD's are evidently generated  in the  process while OCDD's
           are reduced.  This  determination  is based  on  an assumed ash
           generation rate of  5 g/hr  and sludge feec  of  79 g/hr.  Wood inputs
           were not analyzed for  CDD  or  CDF, but are  assumed mino>- compared to
           pentachlorophenol sludge waste.

       9   The highly toxic isomer 2,3,7,8-TCDD has not  conclusively  been
           demonstrated as present and  apparently is  not in  ash samples.  See
           Appendix C for reported mass  fragmentography  and  synthetic isomer
           standard curves.

       »   The toxicities of CDDs and CDFs  are quite  isomer-specific  (see
           table 34).  Thus, data useful for risk analysis must contain  isomer
           data that is clearly independent of contamination.  Staff  chemists
           for all the 1 •'bs are quite confident of  the reliability of their
           reported values especially  in light of tne use  of standard isomers.

       «   Values determined are  in the range reported for combustion ash and
           especially of wood  preserving waste ash  from other sources — see
           table 35.  The fractions of bottom ash/^yash have TCDD values
           similar to values reported for precipitator/down  stack a^h
           fractions in Germany — both  in  level and  increasing ratio with
           smaller size.

       a   Ratios of TCDD/CDD  and OCDD/CDD of the feed sludge (0 and  .74-.76
           respectively) and penta in oil  (0 and .82 respectively) are typical
           of other penta environmental samples but also differ from flyash
           ratio enough to indicate composition changes.

       e   Keasurements of  I^IDD, DCDD, and TrCDD monoi.iers  are significant as
           this is only U.2 second time combustion  sources measureme,  _s nave
           had positive val ies  reported.

       •   Toluene extraction may yield a cleaner concentrate than benzene,
           strengthening the apparent reliability lab C values.
                                       68
                                                                                          jl ,.  li-fiii-a
-------
       •   Recovery of spikes  is  dependent on both  spiking  isorv;er and time of
           spike in the procedure.  These were not  similar  for  the  three labs,

Other information on COD/CDF analysis  and procedures  is provided  in  fhe
Appendix C.

                   TABLE 34.   ACUTE TOXICITIES 01- OIOXINS (7)
                                                  LD50  (ng/kg)
  Substitutions with chlorine       Guinea pigs         Mice        Rats
         None                                       <50 x 103      >l x 10
         2,8                         >300,000
         2,3,7                        28,440          >3,000       >1 x 10°
         2,3,7,8                       0.6-2.0           283.7        40
         1,2,3,7,8                         3,1           337.5

         1,2,4,7,8                     1,125.0        >5,000
         1,2,3,4,7,8                      72.5           825'
         l,2,3,6,7,t                  70-100           1,250:
         1,2,3,7,8,9                  60-100          >],440
         1,2,3,4,6,7,8                 7,180

         1,2,3,4,5,7',8,9                            >4 x 106
         Hexa (mixture)                                            ~1 x
         Oct.a (r.ixture)                                            ~2 x 1G5
     Interperi toneal
                                       69
                                                                                 2
-------
TABLE 35.  COMPARISON  OF  COD  VAUES IN ASH REPORTED FROM COMBUSTION SOURCCS^6

Reporting source
This project (Plant A)
Lab A (d-2)
Lab A td-3)
Lab A (d-4)
Lab C (d-2)
Bottom ash
Saghouse (fly)
Multiple sources wood
preserving waste ash
Lab combustion of
penta (smoke)
Lab combustion of
penta, 2,4,6 tri-,
and 2,3,4,6-tetra-
chlorophenol (ash)
Dow Chemical
Oil/coal combination
Tar burner
Tar, gas kiln
Oil combustion (Swiss)
Municipal Incin-
erator (ng/m3)

TCDD

4
.8
3.3

10
960


5.2

17




38


100



PCDD HXCDD

32 81
2.6 8.7
6 10

20 40
1,400 2,000
9-27

14 56

58 74




2
8
3
160 180



H CDD
(,g/g-
117
42
4

100
640
90-135

172

18




4
92
32
130



OCDD

198
96
1

140
210
575-2,510

710

6




24
300
230
40


TCDD
CDD

.009
.005
.10

.032
.18
0

.005

.1




.56
0
0
.16


OCDD
CDD

.45
.61
.032

.45
.04
.8-. 9

.74

.035




.35
.75
.87
.066


New York (ng/m3) 40-120
Swiss
Canada
Japan

Germany
Precipitator ash
2
9



25
8 30
15 13




60
3




120
.4




.009
.22
.078
.19


.55
.010
.31
.29


Downstack ash 300,000
(ng/m3) (15,
000)





                                                                     '^^iXzSu^^.j!
-------
                                    SECTION y

              EVALUATION OF  FUGITIVE  EMISSION AND RESIDUt" SOURCES
       For the purposes of  this  program,  fugitive materials  are defined as
residues fron*:

       e   Solids settled  in  unlined  lagoons

       •   Spillage  and drippage from treating  cylinders

or emissions from:

       •   Vapors released  from  the treating cylinder during unloading and
           charging  operations

       «   Vacuum vent exhaust during  the  treating cycle

       9   Emissions derived  when  removing  the  accumulation  of treating
           solution  from valves,  fittings,  or open processing vessels

These sources of materials  are of  concern  because of the opportunities for
employees to contact the toxic compounds  before dilution and because of their
impact on ambient air quality or future  land use.

       When the treating cylinder  (retort)  is opened, any treating solution
 eft in the vessel may spill  onto  the  ground.   If the retort is surrounded by
a spill berm, the treating  solutions  are  recovered and recycled to the
system.  However, if the treating  solution  is allowed to fall onto the ground,
housecleaninq activities could result  in  an accumulation of  hazardous waste
material.  Similar minor waste accumulations occu~ fro-n fhe  solids fallout in
unlinpd lagoons or holding  ponds.  The slow buildup of residue in large
wastewater treatment lagoons  can accumulate and remain hdzardous after the
       is abandon — see Section 5.3.
       Low-mo 1 ecu 1 ar-weight organic compounds vaporize  in the retort during
the high- temperature preservative application.  During  marge changes, these
organics are released as fugitive emissions throuoh t~e open door of the
retort, forming a dense white plume.  The woe 1 removeJ  from the retort also
emits material  as a white plume that may exceeu 40 percent opacity after
20 minutes.  Qualitative and semi-quant" tative organic  analyses 1 or speci
pollutants in these emissions were expected to show th2 presence of benzc.
toluene, phenol  and similar volatile arj lew-mo1 ecu 1 ar-weight compounds.
                                       71
                          ^^                   fciuSJ^Jtta&^-TtflJiffij^k^
-------
       Emissions from the  vacuum  exhaust  and  other retort vents also are of
concern.  Source tests at  one  mill measured 2.2 q/m3 (0.^5 grain/scf) of
aerosol in 12.5 m3/min (440  sc.'m) of  gas  from a vacuum pump vent.  Steam
conditioning released 44 g/m-'  of  aerosol  it, a 13 m3/min stream.

       Finally, wnile fugitive emissions  from preservative handling,
transport, leaks, and valves can  occur, no qualitative or quantitative data is
available to characterize  such emissions.

       This section presents the  component speciation results from fugitive
emissions tests conducted  at plant A  and  residues from plant B.  Emissions
from preservative handling,  transport,  leaks,  and valves were not tested.
Also the subjects of chemical  losses  from treated material or runoff from
contaminated surfaces was  not  covered.

9.1    TREATING CYLINDER SPILLAGE AND DRIPPA6E

       The treating facility tested employed  two treating cylinders, and used
penta and creosote preservatives.  Samples of  accumulated spillage and
drippage were collected at the bottom of  the  pent" and creosote treating
cylinder access doors.  Waste  liquid  was  intercepted after falling from the
cylinders but prior to ponding on the ground  beneath.  Two samples were
obtained at each location  at the  beginning and after the field test period.
Table 36 presents the qualitative organic analysis for these samples.

9.2    FUGITIVE EMISSION DURING UNLOADING AND CHARGING OPERATIONS

       Air samples were collected during  unloading and charging operations
directly above the penta and creosote treating cylinder access doors.
Sampling was performed 'ising the modified EPA Method 5 train and XAD-2
cartridges described in Appendix A.

       Fugitive emissions  released through the open cylinder door during
charge changes appeared as a dense white  plume which persisted throughout the
sampling.  Table 37 presents the qualitative  organic analysis for these
samples in concentration per volume of  air sampled.  It >vas not feasible to
quantify a mass emission rate  due to  large fluctuations in ambient air
dilution caused by changing wind  speed  and direction.

9.o    VACUUM VENT EXHAUST

       Certain wood treating processes  require the application of pressure and
vacuum at various steps of the treating cycle.  The pressure release and
vacuum exhaust are sources of  fugitive  emissions, both aerosols and vapors.

       Emissions from a vacuum vent common to the penta and creosote treating
cylinders were characterized.   The frequency  of such emissions is variable but
less than 10 percent of the treatment period.  During the course of a single
treating cycle at this facility, the  chronological sequence in Tabie 33 was
observed.  Grab samples were analyzed onsite  for total hydrocarbons (THC)
                                       72
-------
TABLE 36.  CHARACTERIZATION OF PENTA AMD CREOSOTE TREATING
           CYLINDER SPILLAGE AND [PJPPAGE
Penta treating cyl inder
Sample location: spillage and drippage
Date collected:
Compound
Pentschl orophenol
Phenol
FT uoranthene
Naphthalene
Ben zo( a) anthracene
Benzof a)pyrene
Benzof luordnthenes
Chrysene
Acenaphthylene
Anthracene
Benzo(g,h,i )perylene
Fluorene
Phenanthrene
Di ben zo( a, h) anthracene
Indeno(l,2, 3-c,d)pyrene
Pyr jne
Benzene
Toluen?
Ethylbenzene
9/23/80

1,500
ao
29
50
60
50
54
50
16
47
<10
110
150
<10
<10
24
<0.5
<0.5
<0,5
9/25/30
Concentr
2,100
UO
180
200
80
5.6
26
85
11
55
<5
140
320
<5
<5
140
0.1
C.5
0.5
Creosote treating cylinder
spi 1 1 age and drippage
9/23/80
'ations in ug/g
390
<20
420
1,300
870
240
700
710
72
1,200
<50
1,100
2,300
<50
<50
370
0.3
<0.2
<0.2
9/25/80

1,800
<10
200
1,400
1,000
200
500
850
180
1,500
40
2,600
2,200
20
52
1,700
15
<1
<1
                            73
-------
     TABLE  37.   QUALITATIVE ORGANIC ANALYSIS RESULTS FOR FUGITIVE EMISSIONS

Sample location:
7 i;n number:
Compound
Pentachlorophenol
Phenol
Fluor anthene
Naphthalene
Benzo(a)anthracene
Benzo(ajpyrene
Benzof luoranthenes
Chrysene
Acenaphthylene
Anthracene
Benzo(g,h,i )perylene
Fluorene
°henanthrene
Dibenzo( a, h) anthracene
Indeno(l , 2,3-c,d)pyrene

Ptinta
1

treating
2

cyl inder
3
Creosote
treatincj
cyl inder
1
Concentrat ion*
<0.02
<0.02
0.026
0.057
<0.02
<0.02
<0.02
<0.02
0.13
0.026
-------
TABLE 38.  TREATING CYCLE SEQUENCE

Treating Cycle
Pressure
or vacuum Ter(i.
(atmosphere) °r (°C) Time started
Time completed Lapse tii.ie (hri)
CONDITIONING
1.
2.
3.
4.
5.
Steaming
Vacuum
Preservative In.
Heating in Oil
Preservative Back

23 in. (.77) 8:15 am
5:45 am
210 (99) 6:15 am
. 10:15 am

10:15 am
6:15 am
10:15 am
10:45 am

2.00
.83
4.00
.83
TREATING
6.
7.
8.
9.
10.
11.
i2.
13.
14.
15.

Initial Vacuum
Initial Air
PreservativR In
Pressure Conmenced
Preservative Bai_k
Final Vacuum
Recovering Drippings
Secondary Steam
Secondary Vacuum
Changing Time


70 ps1 (4.8) '0:45 am
11:00 am
90 psi (6.1) 200 (93) 11=;0 am
210 (99) 1:30 pm
23 in. (.77) 2:00 pm
4:00 pm



TOTAL TIME

11:00 am
11:20 am
1:30 pm
2:00 pm
4:00 pm
4:15 pm





.42
.55
2.28
.83
2.00
.42


.42
11.0
-------
            TABLE  39.   SUMMARY OF  TOTAL HYDROCARBON DETERMINATIONS
          Penta pan     Creosote pan
Emission   evaporation   evaporation
 Point     device        device
                                      Penta
                                      treating
                                      cylinder
                                      fugitive
                                      emission1;
Creosote
treating
cylinder
fugitive
emissions
                                                                         Vacuum vent
                                                                Penta cycle
                            Creosote  cycle
 Date                        ppra*  total hydrocarbons as  methane  (tlmo cf day)**
9/23/80 444 C326)
9/24/80 —
— •
892 (1730)
36 (1747)
__
3,660 (1326) 616 (1519) -
984 (1351)
1,790 (1425)
9/25/80     16r> (1250)   1,460 (1450)
           185 (1305)   1,440 (1514)
221 (0828)    42,100 (1034)   22,100  (1332)
365 (0914)    52,300 (1052)   41,500  (1349)
 *ppm =  parts per million
4*(tirae)  =  time s^ample was collected, 24-hr clock
-------
      TABLE 40.   SUMMARY OF SPECIFIC  LOl.'-MOL'ECULAR-WEIGHT  HYDROCARBON
                 DETERMINATIONS AT A  COMMON  VACUUM VENT

Date
(Emission Time
points) (24-hr c


Benzene*
1 ock )


Toluene



Ethyl benzene

Sum of
specific
hydrocarbons
as methane

(penta thermal evaporation device)
9/23/30 1650
9/25/80 1250
1305
(creosote thermal
9/24/80 1730
1747
9/25/80 1450
1514
1.6
ND
ND
evaporation device
ND
ND
ND
ND
ND
ND
ND
)
ND
ND
ND
ND
ND
ND
1.8

ND
1.5
13
13
4.6
ND
6.9

ND
5.8
53
53
(penta treating cylinder fugitive emissions)
9/24/80 i;-2b
1351
1425
(creosote treating
9/24/80 1519
2/25/80 823
914
(vacuum vent d'.-'in
9/25/80 103.'.
1052
ND
ND
ND
cylinder fugitive
ND
ND
ND
g penta cycle/
ND
104
ND
ND
ND
emissions
ND
ND
ND

1,570
1,480
ND
27
11
)
ND
3.3
2.1

1,610
1,720
ND
110
43

ND
13
8.6

11,600
12,000
(vacuum vent ouring creosote cycle)
9/25/80 1332
1349
1,310
1,300
42
64
1,620
1,600
10,100
9,960
*Hydrocarbon units 1.; ppm
ND    not detectable
                                        77
-------
using the procedures described  in Appendix A.  Table 39 presents a summary of
the results of the THC analysis during both  penta  and creosote treating cycles.
       Grab samples of emissions from the vacuum vent also were analyzed for
specific low-mclecular-weiqht hydrocarbons:   benzene, toluene, and
ethylbenzene.  These components were measured onsite using the methods and
procedures described in Appendix A.  Table 39 presents  a summary of the
analyses for specific low-molecular-weight emissions during pcnta and creosote
treating cycles.  These data show that significant  concentratic s of organic
compounds are emitted to the atmosphere.

       From Table 38, it can be seen that a  vacuum  was  drawn for a total of
4 hours, and the retort was open for a total  of 50  minutes.  Based on these
emission periods and the data contained  in Table 39, emission quantities can
be calculated.  Of these quantities, .he vacuum vent represents the greatest
emission source.  A fiald estimated vacuum vent exhaust of 12.5 sm^/mii, (see
Appendix A) with an organic concentration of 42,000 ppm as methane — Table 39
.042 x 16 x 273/22.4 x 298 = 0.027 g/T  result, in  an emission rate of
340 g/min.  For a plant operating weekday: with two retorts emitting for a
half hour per charge, the annual emission rate would be 5.3 metric ton per
"^ar.  By comparison, a medium-sized oil refinery may emit, fugitive VOC as
much as 1,000 metric ton/year^.  Therefore,  though  these concentrations of
organics may cause localized problems, the total emission burden is small
compared to some other sources.

9.4    SETTLED SOLID RESIDUES

       The final disposal of residues that accumulates  is treatment lagoons,
holding ponds or tank depends on site specific management practices.  When the
equipment is part of the processing plant the accumulated material is
frequently recycled if possible.  Contrarily holding lagoons and spray ponds
may only occasionally be cleaned or else residue i.^y accumulate until the
lagoon is bypassed for some alternative  devise.  In the latter case, residues
may require removal to prevent  impacting future land use.  For the field sites
surveyed plants A and C currently transfer residual sludge or ash to on-site
landfills by direct hauling.  Plant B's  residue impacts the environment as a
continuous minor land application is affected indirectly through lagoon bottom
buildup.  The character of tnis material is presented in Tab!.: 41.  Plant  A
had a similar prior practice that was abandon for evaporati-  .

       Without more samples than were analyzed no truly representative numbers
are available to quantify the balance of materials  between water and
sediment.  However, the high values of components in Table 41 indicate that
incoming waste eventually decreases in concentration while the bottom sludge
increases.  As discussed in Section 6,  higher molecule" weight organics are
not emitted very rapidly at low temperatures.  Thus it  is assumed that toxic
organics are settled out of the wastewater onto the laqoon bottom and remain
for some period of time.  Residues are thereby slowly transferred to land
albeit with undocumented environmental  effects.
                                       78

-------
            TABLE 41.  LAGOON SETTLED SLUDGE COMPOSITION
Component             Plant 8 ug/q      Plant A (Abandon Pond)  ug/g
Pentachlorophenol        15,000



Phenol                       <50



Fluoroanthene             5,800



Naphthalene               1,500



Benzo(a)anthracene        2,600



Chrysene                  2,0r'0



Anthracene                1,700



Fluorene                  5,600



Phenanthrene              9,000



Pyrene                    4,400



Other PNAs                  490



COD                           2.1                2.2



CDF                           1.4                0.4
-------
                                  REFERENCES
1.  Environmental Protection Agency "Timber Products Processing Point Source
    Category Effluent Limitations Guidelines, Pretreatment Standards and New
    Source Performance Standards" 40 u^P, Part 42:9 44 FR GPSIO-S^O
    (October 31, 1979) and 46 FR 8260-245  (January  16, 1981).

2.  DaRos, B. et al., "Wood Preserving Industry Multimedia emission
    Inventory" EPA 600/2-01-066 (In press),

3.  Thibodeaux, L. 3. "A Test Method for Volatile Component Stripping of
    Waste Water" EPA-660/2-74-044 (May 1H/O.

4.  Thibcdeaux, L. J  et al., "Measurement of Volatile Chemical Emissions
    from Wastewatar Basins" EPA IERL (draft).

5.  McAlister, J. A., B. G. Turner and P..  B. Estridge "Ti eatment  .  S.'1e:ted
    Internal Kraft Mill Wastes in a Coding Tower"  EP'v-12040 EEK (August
    1971).

6.  Harris, J. C. et al., "Uior.in Emissions from Combustion Sources:  A
    Review of th^ Current Stace of Knowledge" A. D. Little -Inc. report to
    ASME, Camoridne, MA, n-jcembsr 29,  I98C.

7.  Esposito, M. P., T. 0. Tiernan and F.  E. Dryden, "Dioxins"
    EPA-600/2-80-197 (November 1980).

8.  Radian Corp: "Control Techniques for Volatile Organic Emissions from
    Stationary Sources" EPA-450/2-78-G02 (May 197°).
                                      BO
-------

                                   APPENDIX A

          CHARACTERIZATION OF MULTIMEDIA EMISSIONS FROM THERMAL (PAN)
                   EVAPORATION OF WOOD PRESERVING WASTEWATERS
       Raw data for this study has been compiled and is available upon
request.   That data covers the source emission sampling for high-molecular-
weight, and total hydrocarbon, and specific low-molecular-weight
determinations.  Copies may be obtained from EPA-Industrial Environmental
Research Laboratory, 26 W. St. Clair Street, Cincinnati, OH.

A.I    TEST SITE

       Tne wood treating facility tested is decribed in Section t> with a
schematic of the plant wastewater/preservative recovery system shown in
Figure 1.  The treated product amounted (17,320 ft-3) 490nr to during the
July 22 to 25, 1980 field test period.  Table A-l oresents a summary of the
production components during the field test.

A.2    FIELD TEST PROGRAM

       The following subsections describe the equipment and techniques
employed during sampling.


             TABLE A-l.  SUMMARY OF TREATING PRODUCTION FOR THE
                         PERIOD JULY 22 THROUGH JULY 25, 1980
                 Treated                5i Penta
                 Product               Liqht Oil       Creosote
                                           ft3       m3      ft3
Uti lity poles
Posts
Lumber
Pil ings
42.6
113.6
118.4

1,509
4,012
4,130



178.9
37.0


6,318
1,306
               Total            274.7      9,701     215.9    7,624
                                       81
-------
l^fBWgiifffi!^
    A.2.1  Source Emission Sampling of Pan Evaporation Devices

           Sampling of high-molecular-weight organic emissions from the pan
    evaporator outlet, was conducted using the EPA Method 5 sampling train
    nonisokin°tically as shown in Figure A-l.  The train consisted of a heated
    1/2-inch O.D. Teflon sample line connected to an empty Greenberg-Smith
    impinger (witnout an impaction plate), followed by the XAD-2 resin cartridge.
    The resin was followed by a second Greenberg-Smith i~pinger containing 100 ml
    of deionized water.  The third impinger, an empty Green&erg-Smith without an
    impaction plate, was followed by a silica gel desiccant (SiOp) trap to
    protect the vacuum pump and sampling control module from moisture.

           Four complete source tests were conducted at the penta (pan) thermal
    evaporator and at the creosote thermal (pan) evaporator.  The evaporators and
    sampling locations are shown in Figures A--2 and A-3.  Fcr each source test,
    the sampling equipment was placed on the roof of the thermal (pan) evaporator,
    the Teflon sampling line was allowed to preheat to approximately 250°F, and
    the impinger train was prepared.  Sampling was started by turning on the
    vacuum pump and opening the coarse adjusting valve to its midpoint.  This
    valve position was maintained during the entire sampling period.

           The volume of condensate determined the possible sampling times.  As
    the first impinger filled with water, control of the sampling rate was lost.
    The sampling run was terminated by shutting off the vacuum pump, disconnecting
    and sealing the inlet and outlet of the Teflon sample line, and moving the
    train to the field laboratory.  Table A-2 presents a summary of the pertinent
    source sampling parameters at each test location.

           Samples were transferred from the sample trains to specially cleaned
    and labeled storage containers.  The probe nozzle, probe, and connecting lines
    were rinsed with methylene chloride, and the recovered samples transferred to
    the appropriate storage containers.  Immediately following sample recovery,
    all samples were iced in the field and maintained under those conditions for
    their transport to the analytical laboratory.

    A.2.2  Source Emission Sampling of Penta arid Creosote Treating Cylinders

           Sampling of high-molecular-weight emissions during the unloading and
    charging of the penta and creosote treating cylinders was conducted using the
    same procedures and methods described in section A.2.1.  The sampling
    locations are shown in Figures A-4 and A-5.  Sampling was initiated a few
    minutes prior to opening the cylinder door and terminated a few minutes after
    the door was closed.   Sampling times varied from 11 to 21 min and were
    dependent upon the size of the charge being unloaded or loaded and the ease
    with which the operation proceeded.   Table A-3 presents a summary of the
    pertinent source sampling parameters for each test.

    A.2.3  Total  Hydrocarbon Determinations

           Total  hydrocarbon sampling was conducted at the outlet of the penta and
    creosote thermal  (pan) evaporators,  the penta. and creosote treating cylinders
                                           82
-------
  Heated  leHon sai.'plimj line



ff	—
                                                                       XAD-2 tr«p
\   Dry gas rr
-------
F1
       A-2.  Photograph of penta then,*] (pan) evaporator and sample location.
-------
00
•-
                             Figure A-3.  Photograph of creosote thermal  (pan)  evaporator
-------
                 TABLE A~Z.  SUMMARY OF  SOURCE  EMISSION SAMPLING PARAMETERS  FOR  TEST CONDUCTED
                             AT THE PEMA  AND  CREOSOTE THERMAL (PAN) EVAPORATION DEVICES
bjruftrii- Actual

Petit*
fvjp \ 9-23-30 2M.2 13,90
9-24-60 29.2 0.695
9-25-80 rt.4 19.5
9-2&-80 29.5 e.tl
[»p"U" .-:.-:; *.4 u.06
9-24-HO 29.2 27. ?9
9-25-80 29.4 2^.W
9-25-00 29.5 19.4i
Mrti-r
("F)
59.0
63.5
43.5
54.8
5*.3
59.0
89.7
55.5


6, '9
1.300
972
593
622
I.:M
762
945
e Stuk
(•*)
209
215
209
206
191
!93
190
195
Wr-l.jllt
Or v
( 1 L'/ 1 ti -(no IP)
29. 8A
27.84
29.04
29.84
29.84
29.84
?9.84
29.84
f!uli»cul ar
Weight
(lt,/lb-mole)
22.4]
18.13
20.036
20.82
22.39
22.1
n.n
27.78
S. imp 1 I'd
Gas
(',cfm) H?n
19. OR 62.6
0.697 *»..<)
6.50 R2.8
8.8 76.2
17.16 (.1.)
29.02 64.7
23.87 60.1
20.89 68.1
Tot 4!
Sdftp 1 ing
1 1 (M.

50.0
29.0
19.5
15.0
30.0
56.0
45.0
O.5
CO
°^        ^A-^iui^J Ml of air.
-------
CO
          l-r.===-- ^M       I  ^
          W^^^-**m

                        Figure A-4.  Photograph of  penta treating cylinder being charged with
                                    poles and the  fugitive emission vent.
-------
figure A-t>.  Photograph of creosote treating cy) truer buiiuing and
             fugitive emissions vent.
-------
                 TABLE  A_3.   SuW-WRY OF SOURCE t'MISSION SAMPLING PARAMETERS FOR TESTS CONDUCTED
                             AT THE  PENT.A AND CREOSOTE TREATING CYLINDER DURING UNLOADING AND
                             CHARGING OPERATIONS
8arv«.c'.fic Act'-ml*
£ -~ f\*, i/ r * ii=Rfi ](* fV? Lff
i «X 1 1 '• i". ' { in ,ft^ 't | n o 1 i^ar l^^V***" ^l Jf €
!>*•» »^.-wr Gil* ;>.;} (*cf*J If)
PIP Kflarl
i »-;j-ao »"*.-80 rt.40 2?.3S W.O
S.?!»rl; 1 t volutu^ Percent
folj («T) f iti/lb-iuc'e) ()t;/lt>-!W)U) (scfm) H;/0
».i S?.0 ?9.84 2S.19 16.17 13.9
n.1 VO.O Z9.M ?9,1? 21.73 6.M
!j.l 69.0 ?9.fl4 ?9.7? ??.ni 1.0
— 70.0 29. 84 29.84 25.17 0.0
loul
(ruin)
11.0
14.0
16.0
71.0
CO
y-S
-------
during  unloading  and  loading,  and at the outlet of the vacuum vent discharge
to the  barometric  condenser.   Sampling was conducted using the system shown in
Figure  A-6.   The  gas  sample was extracted from the stack via a 7U sintered,
stainless  steel Todel  Mo.  5S-4  FF-.1 filter, manufactured by Nupro Valve
Company, Willoughby,  Ohio.   The filter removed fine particulates which could.
if allowed to pass Into  the THC analyzer, occlude the FID sample inlet
capillary.   A 0.006m  O.D.  stainless steel probe connected the filter unit, to
the heated sampling  line via a  three-way stainless steel solenoid valve.  This
valve introduced  sample  gas or  calibration gas expending on the desired mode
of operation.   A  100-ft, heit-traced,  3/3-inch 0.0.  Teflon sample line
manufactured by Unitherm Company was used to transport the sample to the
vacuum  pump.   The  sample line  temperature was maintained at 394°K by
internal temperature  controllers already installed.   A Teflon-coated diaphragm
vacuum  pump manufactured by Thomas Industries, Sheboygan, Wisconsin, was used
to pull the sample through the  heated line.  From the vacuum pump exit, the
sample  was split  and  routed to  the analyzers via short lengths of heated
Teflon  line.

       Prior to operation  and  calibration, the completed sampling system was
operated at normal line  sampling conditions and purged for several hours with
zero grade nitrogen  to remove  any traces of residual hydrocarbon contamination
in the  lines.   During this "bake-out"  procedure, stainless steel tube unions,
filters and probes were  haated  using a propane torch.  Before and after each
test, a leak test  was performed on the sampling system followed by calibration
of the  THC analyzer  using  zero  grade nitrogen gas and a mixture of 801 ppm
methane in nitrogen.   During calibration, the three-way valve was positioned
to block the sample  probe  and  filter,  allowing the calibration gas to pass
into the heat-traced  sample line.  Introducing the calibration gases at this
location,  ensured  the sample gases and calibration gases were treated in the
same manner,  nullifying  possible undesirable effects due to absorption in the
sampling line and  system.

       A model  400 total hydrocarbon ^THC) analyzer, manufactured by Beckman
Instruments,  Fullerton,  California, was used to continuously monitor total
hydrocarbon emissions from the  vacuum vent discharge.  This analyzer uses the
flame ionization  detection (FID) method.  The analyzer output was recorded
jsing a Model  585  strip  chart  recorder manufactured by Linear Instruments
Corporation,  Irvine,  California.

       The FID was operated using zero grade (<1.0 HC) hydrogen fuel and zero
grade air  supplied by Airco Industrial Gases, Santa Clara, California.
Hydrogen fuel  and  zero air pressure were set at ?07 KPa (30 psi) and 103 KPa
(15 psi),  respectively,  using  internal differential  pressure regulators in the
analyzer.

       After  approximately 1  hour of sampling at the vacuum vent, the heated
sampling line was  heavily  contaminated with hydrocarbons.  Attempts to
recalibrate and rezero the FHC  analyzer were impossible.  At this point, the
heated  bulb method was substituted for the continuous method.
                                       90
-------
                           "„••" sintere.l itjinless steel
                                           o  s 1 4 c k
    Calibrat ion
    gases
                    Three-«i>  stainless


                   Heat triced Teflon  sample line i)C.43n,


                           Heat traced Teflon connect —


'I
rv
J "! inject iori
L-J loop and
U-i L4-J ' te^fl


hydrocart.on
anal y;er


Strio
chart
recorder










TJ
A
rO
O
L.



(
E_






M <
Tft


M
A
o^
^
=


',!
ct-
Go",
I
rip
,*. rt
rt?cOrcter





T




A
l_
•«
0
1_
•*,


<
n


H




„,,



S
CJ
•~
-
L


r— 1
T




'S,
c
k.
3
^
u'.

<
2
h vi'vc

>— I




Figure  A-6.   Schematic of  unburned hydrocarbon and  gas chromatograph
               sampling system.
                                      91
-------
       Grab samples from the appropriate  source  were  collected by evacuating
and purging ?50-rol p}-rex glass sampling Luibs heated  to  l?l°f  (;50°F).
Alitluotes of the collected samples  then were withdrawn  from the heated  bulb
using a 5-mi gas-tight syringe inserted through  a  septum port  in the bulb.
Tf:<" syringe contents were injected  VM a  2-cmJ -injection loop  and bcmkflush
valve into a Varian Model 3700 cas  chro.-nitoqrapn (GC).   GC  operating
condicio.is for THC anal/sis are presentee} in Table A-4.

       Table 3l> prcs2nts a summary  of the results  of  THC determiriatiC'"1: ct  the
various emission points basec on the total  area  c^romatogra^h  and hackf 1-jih.
The results are reported as PPM methane
       The accuracy uf the data presented using  the  heated  bulb method  of
         varies substantially.  The greatest error associated  with  this -nethod
is sample integrity.  It was apparent that samples collected at the penta  and
creosote thermal (pan) evaporators were rrostly water  vapor.   When  these
samples were transfer-red via syringe to the GC for analysis, condensation
aitnin the syringe most 'ikely co-condensed hydrocarbons, thus causing  lower
values than would be expected.  The error is estimated  to be ^ 50  percent
ma* i sum.

       TKC values for samples collected from the  treating cylinders are also
very uncertain due to the nature of the s-jn.pllng  site,   the  fugitive emissions
were prone to large fluctuations in a^
-------
           TABLE A-4.  GAS CHROMATOGRAPH OPERATING CONDITIONS FOR
                       THE DETERMINATION OF TOTAL HYDROCARBONS
Column:


Injector temperature:

Temperature program:

Special ncte:
6-ft x 1/8-inch 0,D. stainless steel tubing packed
with 1 percent SP 1000 on carbopack (80/100 mesh)

120°C

Isothermal at 120°C

Inject 2 cm3 sample for approximately 5 min or
until ethyl benzene component was eluted, then
back-flush until baseline returned to zero.
-------
A.2.5  Liquid Grab Sampling

       Grab samples of  the following  were  collected  during  the  3-day  sampling
period:

       •   Penta  thermal  (pan)  evaporator  contents

       «   Creosote thermal  (pan)  evaporator  contents

       «   Bulk per.ta  in  treating  oil  (before  use)

       •   Bulk creosote  (before use)

       «   Penta  treating cylinder spillage

       •   Creosote treating  cylinder  spillage

       «   Penta  oil/water separator  (both fractions)

       *   Creosote oil/water separator  (both  fractions)

Liquid samples of the  penta  and creosote evaporator  contents were co'Mected  in
the morning and afternoon of  each  sampling day.   Samples  were collected by
lowering a precleaned  sample  container  into the evaporator  tank arid retrieving
the liquid near the surface.

       Samples of liquid  fractions contained  in the  penta and creosote primary
oil/water separators were obtained on  a daily  basis.   Samples were obtained  by
immersing an  inverted  sample  container  into the appropriate  layer then tipping
it to collect the sample.  Some contamination  was observed  during retrieval  of
the lower fraction; however,  this  was  minimal  with respect  to the initial
sample volume.  This will bias  the creosote wastewater values to the  high
side, and the penta recycle oil to the  low side.

       The remaining samples  of bulk  penta and creosote,  and the penta and
creosote treating cylinder spillage, were  collected  on a  one-time basis.
After collection, all  samples were immediately iced  and maintained on ice for
transport to  the  analytical  laboratory.

A. 3    ANALYTICAL METHODS

       Samples from the thermal (pan) evaooration system  were received on
Octotr-1" 21, 1980.  The  samples were assigned consecutive  laboratory
identification numbers  and stored  at 4°C until analyzed.

A.3.1   Analytical Methods

       Analyses  were conducted for   >latile orqanics, semivolatile oraanics,
and dioxins.   Volatile organics analyses were  based  on variations to EPA
Method 624.   Semivolatile organic  (phonols and polynuclear  aromatics) analyses
were based on sample preparation variation to  EPA Method  625 in conjunction
-------
with fused silica capillary column gas chromatography/wass spectrometry
(GC/MS).

Analysis  of Volatile Organics —
       The analytes of interest were benzene, toluene, and ethylbenzene.  The
sludge and waste.-.ater samples were analyzed for these components.

       A  l.Og aliquot of the mixed sludge or wastewater was weighed into a
i5-ml crimp top vial.  Pentane (9 ml) and l-bromo-2-chloropropane (lOyg) were
added as  internal standards.  A l-ul aliquot of this diluted sample was
injected  in a 0.2 percent Carbowax 1500 on a Carbopack C packed GC column in a
Finnegan  1020 GC/MS instrument.  Analysis and quantitation were conducted per
EPA Method 624 using the internal stnadard method.

       Quality control for the volatiles analysis entailed the anlysis of
method blanks and method standards spiked at 10 ug/g of sludge.  In addition,
the control requirements of Method 624, including instrument tuning to meet
specifications, were met.

Analysis  of Semivolatile Organics —
       Semi vol ati le organics analyzed are listed  in Table A-5.  These analy^.s
were conducted by variations to EPA Method 625.  The variations were in the
sample preparation and in the use of fused silica capillary column GC/MS to
determine these compounds.
Sample Preparation —
       Sludge samples were prepared as follows:

       1.  Place 10.0 g of the sludge in a clean 250-ml brown bottle.   Add
           10.0 g of anhydrous sodium sulfate and 100 ml of pesticide grade
           dichlormethane,  Shake occasionally and allow to sit overnight at
           room temperature.

       2.  Take 1.0 ml of each extract for GC/FID screening.  Store the
           remaining extract at 4°c.

       3.  As required by the GC/FID screening, filter the extract into a
           Kuderna-Danish concentrator and concetrate to 1.0 ml.

       The GC/FID screening stage was necessitated by the wide variability of
r-ample concentrations.  Figure A-7 summarizes the semivolatile scheme for
sludge samples.

       The XAD-2 cartridge was carefully opened, any silicone stopcock grease
removed with a Ch^Clj wetted towel, and the contents transferred to a
preextracted Soxhlet thimble.   The XAD-2 mate, ,al in the Soxhlet was spike
with surrogate mix and extracted overnight with
       To  assure analysis of all  organics collected during the XAD-2 sampling,
two other  samoles v;ere taken for  each sampling c. ain:   a dichloromethane probe
rinse and  an  impinger catch.  For analysis, the dichloromethane rinse was
added to  the  XAD-2 soxhlet extractor.  The impinger water was acidified to
                                       95
-------
TABLE A-5.  SEMIVOLATILE ORGANICS ANALYZED  IN UOOD PRESERVING SAMPLES
               Number                     Name
                  1             Phenol



                  2             2-Nitrophenol



                  3             2,4  Dichlorophenol



                  4             2,4,6  Trichlorophenol



                  5             4-Nitrophenol



                  6             4,6-Dinitro-o-cresol



                  7             Pentachlorophenol



                  8             Acenaphthalene



                  9             Fluoranthene



                 10             Naphthalene



                 11             Benz(a)anthracene



                 12             Chrysene



                 13             Acenaphthylene



                 14             Phenanthrene



                 15             Fluorene



                 16             Pyrane



                 17             Benzofluoranthenes



                 18             Benzo(a)pyrene
                                  96
-------
        ICg  sampl;
      Dry  (Na-SO.)
      and  extract with
      10  fold  CH0C10
      Screen dilute
      extract by
      GC/FIB
                           All  peaks
                           in  linear
                           GC/MS  range?
              Greatest peak
              greater than
              500 ug/ml?
       Dilute
       extract x 100
      Proceed to FSCC
      analysis
All peaks
less than
10 ,.g/ml?
      Concentrate
      extract x 100
Figure A-7.  Analysis scheme for phenols/PAHs in wood preserving
             sludges.
                               97
-------
pH 1 w .h 6N H?S04 and extracted overnight in a continuous liquid-liquid
extractor.  The water extract and XAD-2 extract were then combined, dried with
anhydrous sodium sulfate, and concentrated to 1.0 r,\l.

       Quality cor:frol for XAD-2 samples consisted of the analysis of
surrogate spikes, f.eld blanks, and spikecl method blanks.

Extract Analysis —
       Each of tne extracts obtained as described in the previous section was
analyzed for the compounds listed in Table A-5 using fused silica capillary
colunn GC/MS.  The instrument operating conditions also are listPd in
Table A-6.

       Tne quality control requirements listed in EPA Method 625 were
followed, incl-iciirig analytical calibration, mass spectrometer tuning to meet
decafluorotriphenylphosphine (DFTPP) criteria, and the use of multiple intenal
quantitation.  The internal standards used were dg-naphthalene,
d^Q-anthracene, and d^-chrysene.

A.3.2  Analytical Results and Discussion

Volatile Organics—
       Volatile orqanics  (benzene, toluene, ethylbenzene) were determined i'.
water and sludge samples  using a pentane extraction method followed by GC/MS.
Figure A-8 is a chromatogram of a method blank spiked with the compounds of
interest at 1 pg/g.  The  solvent contaminants did not interface with the
dptemination of the compounds of interest.

       Figure A-9 is a chromatogram from the analysis of a retort drip
sample.  This sample is typical, having very low or no detectable volatile
aromaocs.  No contamination was detected in the analysis of method blanks.
It was, however, necessary to increase the column bake cycle time after the
injection of several samples because higher-molecular-weightr creosote
components accumulated on the column and performance deteriorated without the
extra bake cycle.

Semivolatile Orqanics—
       Phenols and polynuclear aromatics were determined by solvent extraction
and fused silica capillary column GC/MS.  An extract prescreening procedure
using GC with FID determined the appropriate extract concentration factors
prior to GC/MS analysis.  "I he prescreening was especially important with
certain sample types (oil/water separator samples) which were extremely
variaole in content.

       Two ca^es of contamination were detected during the course of the
study.  The XAD-2 blanks contained 10 to 200 ug of naphthalene.   This is an
XAD-2 contaminant as received from the manufacturing process and indicates an
insufficient washing process prior to field sampling.  Ony trace levels of
other arsalytes (1 to b vg) were detected on the XAD-2.  During the GC/MS
injection of a series of thick creosote extracts, a serious
cross-ccntamination was detected,.  As much as 0.1 percent sample-to-sample
                                       93
-------
       TABLE A-6.  F'JSED SILICA UPILIARY COLUMN PARAMETERS
Column:

    30rn x 0.2C n SE-54 k'COT (JS.V.1 Scientific)

Split]ess Injection Parameters:

    Injection mode:           Solitless
    Sweep initiation:         30 sec
    Sweep flow:               Greater than or equal to 12 ml/min
    Column flow (He)
    measured at
    atmospneric:              1.0 ml/min

Interface:

    Temperature:              300°C
    Column directly coupled to source (no transfer lines)

    Temperature Program:

        Initial:              30°C for 2 niin
        Program.-              Ramp to 300°C & 10°C/min
        Hold:                 300°C, 15 min

    Mass Spectral Parameters:

        lonization mode/
        energy:               Electron impact/70 eV
        Total scan time:      1,0 sec
        Mass range:           35 to 475 AMU
                                99
-------
iw.e-
 PIC
RtC
ei-05'81  15il3:09
SAMPLE: «8?-13-ei5-8 UOfl.lUL  IMJ .(5F=l.g
RwHGE: G  I. <99  LBBEL: fl  1?. -1.0 OU«H: A  0,
     S5
                                                                s «1
                                                                HI
                                                          BH'E: U 2fl.  3
                                                                               SCflMS
                                                                                      i ro 4.10
                                                                            Peak  Identifications:
                                                                              C
                                                                              IS
                                                                      Solvent Contaminant
                                                                      Internal Standard
                                                                      Benzene
      Figure  A-8.   Total  ion  current chromatogram  of  a  volati'les standard.
                                               100
-------
183.9-1
                                                       DATA: P5T02 »1
                    16:28tP»                            COL1- Fi'4i HI
            SAMPLE: ST02.ftMTiWE WM,llA.= ieNG EftCH CHPO
            P3NGE: G   1- 40(3  LAPEL: H  0.  4.0  OIMN: A 0, 1.0  f«£E:  U 20.
                  bo
SCANS
        1 TO  40r.
                                                                            Peak Identifications:

                                                                             B  « Benzene
                                                                             C  " Solvent Contaminant
                                                                             E  « Ethyl benzene
                                                                             IS •" Internal Standard
                                                                             T  - Toluene
                                                                                 E
                                                                                3F.il
       Figure A-9.    Total  ion  current chromatogram  for  a retort drip
                         volatiles  analysis.
                                             101
-------
contamination was detected v.hen usino l-ul capillary syringes.  No method for
routine cleaning of these syringes could be found.  However, no such problem
was detected with standard 10-ul syringes.

       In the dirtipst creosote samples, the overall retention time of many
compounds varied from that measured in the standards.  However, the retention
time relative to a nearby eluting internal standard was a reliable
indentification criterion.  Special care was needed with the benzo(a)pyrene
isomers.  Figure A-iO shows the M/F. 126 and 25L exracted ion current profiles
for one of the creosote samples.  Although standards were not available, the
other isomers were tentatively  identified as listed.  The two
benzofluoranthenes could not be reliably separated  in the presence of so many
other compounds.  It was decided to report these tivo as a single value for all
samples.

       Figure A-ll shows the chromatograms from various spots in the creosote
preserving process.  A few of the major peaks are identified in eacn
chrcmctogram.  The creosote at this plant appears to be different from other
creosotes in that the phenol content is very low (400 ppm).

       Table A-7 presents a Icj of all samples collected, followed by
Tables A-8 through A-21 which present the analytical data.

       Figure A-12 shows samples from the pan evaporation process.  It is
clear that the liquid left behind in the evaporator is concentrated in the
high-molecular-weight polynuclear species such as chrysene and
benzo(a)pyrene.  These polynuclears do not volati?e to the same extent as the
low-molecular-weight species.  Figure A-12(d) is a chromatogram of an XAD-2
blank extract.  Of the compounds of interest, only naphthalene was detected i,.
the blank.  Duplicate blank samples showed 100 and 140 pQ of naphthalene.  The
XAD-2 cartridge extract shown in (d) is an 8,000-fold dilution of the total
extract.  The quantitative result for this sample wa 2.8g of naphthalene for
the iOg sample.

       Chromatograms for penta process samples are shown in Figure A-13.  The
use of petroleum distillate as the penta vehicle complicates the chromatograms
immensely, since it also contains polynuclear aromatic hydrocarbons.  The
concentration of penta in these samples, however, was sufficiently high for
reliable quantitation in the presence of the oil matrix.  For lower
concentations than seen here, an adJHional sample preparation of neutrals
from acids would be necessary.

       Figure A-14 shows chrcmatograms from the penta wastewater evaporation
process.  Penta was detected in the XAD-2 cartridge.  However, the
hydrocarbons appear to the preferentially evaporated as evidenced by the
concentration of penta in the pan bottoms.   No contamination from penta was
seen in XAD-2 blanks.
                                      102
-------
SIC  • X.-SS O^CWiA.HjWft                         DA1A: AM '. VI Utt
CI.VO'tM 
-------
                                   i a o. I.ft BuSLt U J
             (a) Creosote oil/water separator  —  top  layer
               •_ iiJbU^




            (b)  Creosote oil/water separator -- bottom layer



Figure A--11.  Chromatograms of creosote  solutions  through  the  process.
                                 104
-------
                  tt I. A Wit i U J
            I
(c) Creosote working solution
  (d) Creosote retort drips




  Figure  A-1.1.   Concluded
            105
-------
TABLE A-7.  SAMPLE NUMBER AND IDENTIFICATION
Sample No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14

15

16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39

40
Sample Description
Pond, top layer w/oil, 1 of 2
Pond, top layer w/oil, 2 of 2
Pond, sludge
Pond, middle layer
Creosote pan evap. liquid, 1700, 9/23/80
Creosote oil /water separator, top layer, 9/23/30
Creosote oil/water separator, boctom layer, 9/28/80
Creosote retort drips, 1158, 9/23/30
Penta fugitive emission, front half
Penta fugitive emission, back half
Penta retort drips, 1138
Penta oil /water separator, top layer
Creosote pan evap. liquid and impinger HjO, frjnt half
Creosote pan evap. liquid jnd impinger 1 h^O, front half,
rinse
Creosote pan evap. liquid and imoingers 2 and 3 HpO, test 1,
back half, rinse
Creosote oil /water separator, top layer
Creosote oil /water separator, bottom layer
Creosote pan evap. liquid, pretest
Creosote pan evap. liquid, test 2, front half
Creosote pan evap. liquid, test 2
Creosote pan evap. liquid, test 2 probe rinse
Penta pan evap. liquid, test 2 impinger H?0
Penta pan evap. liquid, test 1, front half rinst
Penta pan evap. liquid, pretest 1
Penta pan evap. liquid, test 2
Penta pan evap. liquid, test 1, back half
Penta fugitive emission, test 2, front half
Penta pan evap. liquid, test 2, front half
Penta oil/water separator, top layer
Penta pan evap. liquid, test 1, back half rinse
Penta pan evap. liquid, test 1, front half, impinger t^O
Penta oil/water separator, bottom layer
Penta pan evap. liquid, test 2, impinger H^O
Penta pan evap. liquid, test 4, impinger H^O
Penta pan evap., bottoms from value 6 in. off ground
Penta retort fugitive emission, test 3, impinger H^O
Penta pan evap. liquid, test 3
Penta 40 percent solid in No. 2 fuel oil
Penta retort fugitive emission, test 3, front half, MeCl^
rinse
Penta pan evap. liquid, test 3, fron half, MeCl? rinse
                    106
-------
                            TABLE A-7.  Concluded
Sample No.                         Sample Description


  41         Penta pan evap.  liquid, test 4, front half, MeCl2 rinse
  42         Penta oil/water  separator, bottom  layer
  43         Penta retort drips
  44         Creosote pan evap.  liquid, test 4,  impinger H?0
  45         Creosote pan evap.  liquid, test 3,  impinger HjO
  46         Creosote pan evao.  liquid, test 3,  front half
  47         Creosote pan evap.  liquid, test 4
  48         Creosote retort  fugitive emission,  test i, front half, impinger
             H20
  49         Creosote oil/water  separator, bottoji  iayer
  50         Creosote retort  fugitive eTnisson  test 1, front half, MeCI-2
             rinse
  51         Penta oil/water  separator, top layer and oil
  52         Creosote pan evap.  liquid, test 3
  53         Creosote pan evap.  bottoms
  54         Creosote retort  drips
  55         Creosoxe pan evap.  liquid, test 4,  front half, MeCl.2 vinse
  56         Creosote oil/water  separator, top  layer
  57         Creosote working solution, tank 5  (new)
  58         Penta working  solution, as used
  59         Penta pan evap.  liquid, test 4
  60         MeCl2 blank, baker  res. anal.
  61         Viking D1H20,  all tests after 9/24
  62         Well No  4
  63         XAD, penta pan evap. liquid, test  1
  64         XAD blank No.  2
  65         XAD, penta pan evap. liquid, test  4
  66
  67
  68         XAD, creosote  pan evap. liquid, test 4
  69         XAD, creosote  pan evap. liquid, test 3
  70         XAD, creosote  pan evap. liquid, test 1
  71         XAD, penta fugitive emission, test  1
  72         XAD, creosote  pan evap. liquid, test 2
  73         XAO, penta fugitive emission, test  2
  74         XAD, creosote  pan evap. liquid, test 3
  75         XAD, penta fugitive emission, test  3
  76
                                     107
-------
                    TABLE A-8.  WOOD PRESERVING TEST RESULTS

                                            TEST  CPEOSOTE PAN EVAP  TEST 1

                                            TEST DATE  9/23/80

COMPOUND Acurex I.D. #
80-10-015-
Pentachlorophenol
Phenol
Fluoranthene
Naphthalene
Benzo(a)anthracene
Benzo(a)pyrene
Benzof 1 uoranthenes
Chrysene
Acenaphthylene
Anthracene
Benzo(ghi)perylene
Fluorene
Phenanthrene
Dibenzc( a, h) anthracene
Indeno(l ,2,3-cd)pyrene
Pyrene
Benzene
Toluene
Ethyl benzene
Liquid
-5
2.3
<0.5
7.8
33
15
7.5
13
12
76
12
3.2
50
35
0.7
3.0
6.5
<0.1
0.1
0.5
3W Sep Top i
-6
0.5
15
7.0
30
11
3.9
10
7.6
36
8.2
1.4
25
20
<1
<1
5.8
0.1
0.1
<0.1
CW Sep Bot
-7
360
<100
3500
18000
9800
2400
2200
5300
2200
300
<100
11000
2500
120
<100
680
26
140
44
XAD
-70
0.45
0.08
0.67
2.0
0.009
<0.01
<0.01
0.007
0.061
0.33
-------
                    TABLE  A-9.   WOOD  PRESERVING TEST RESULTS
                                            TEST  CREOSOTE
       JESLJ.
                                            TEST  DATE
9/23/80

COMPOUND Acurex I.D. $
80-10-015-
Pentachlorophenol
Phenol
Fluoranthene
Naphthalene
Benzo(a)anthracene
Benzo(a)pyrene
Benzof 1 uoranthenes
Chrysene
Acenaphthylene
Anthracene
Benzo(ghi)perylene
Fluorene
Phenanthrene
Dibenzo(a ,h)anthracene
Indeno(l ,2,3-cd)pyrene
Pyrene
Benzene
Toluene
Ethyl benzene
Retort'Drips
-8
390
<20
420
1300
870
240
700
710
72
1200
<50
1100
2300
<50
<50
370
0.3
<0.2
<0.2





NOTE:




















Fugitives
y/25/80 w
this XAD
mistake.


















cashes from
re added to
ample by














All  concentrations in units  of micrograms per gram except for  XAD  collections
which are total  milligrams collected.
                                      109
-------
                    TABLE A-10.   WOOD  PRESERVING  TEST RESULTS

                                            TEST      CREOSOTE PAN EVAP
TEST 2
                                            TEST DATE   9/24/80

COMPOUND Acurex I.D. #
80-10-015-
Pentachlorophenol
Phenol
Fluoranthene
Naphthalene
Benzo (a) anthracene
Benzo(a)pyrene
Benzof 1 uoranthenes
Chrysene
Acenaphthylene
Anthracene
Benzo(ghi)perylene
Fluorene
Phenarithrene
Dibenzo(a,h)anthracene
Indeno(l ,2,3-cd)pyrene
Pyrene
Benzene
Toluene
Ethyl benzene
re Test
i<-|U id 8:30
-18
3.4
11
20
13
14
24
5.7
8.9
1.2
9.9
0.6
2.5
3.2
0.9
0.7
16
<0.1
<0.1
<0.1
O.W. Sep Top
-16
12
7
20
42
10
2
4
10
2
1
0.2
16
19
0.2
0.3
15
<0.1
<0.1
<0.1
O.W. SepBot| KAD
-17
3600
1500
33000
33000
23000
610
530
19000
3400
69000
<500
38000
41000
<500
<500
27000
<50
<50
<50
«
i
-72
<0.1
23
38
310
0.6
<0.05
0.08
0.5
11
49
<0.1
170
150
<0.1
<0.1
24
NA
NA
NA
All concentrations in units of micrograms per gram except for XAD collections
which are total  milligrams collected.
                                      110
-------
                    TABLE  A-ll.   WOOD  PRESERVING  TEST RESULTS

                                            TEST   CREOSOTE  PM EVAP
               TEST 2
                                            TEST DATE
9/24/80
ia-jid >>2
COMPOUND Acurex I.D. #
80-10-015- 1
Pentachlorophenol
Phenol
Fluoranthene
Naphthalene
Benzo(a)anthracene
Benzo(a)pyrene
Benzofl uoranthenes
Chrysene
Acerwnhthylene
Anthracene
Benzo(ghi)perylene
Fluorene
Phenanthrene
Dibenzo(a ,h)anthracene
Indeno(l,2,3-cd)pyrene
Pyrene
Benzene
Toluene
Ethyl benzene
-20
13
14
64
18
41
1.7
2.1
26
3.7
26
< 0.4
75
91
0.4
< 0.4
48
< 0.1
< 0.1
< 0.1































































All  concentrations in units of micrograms per gram except for XAD collections
which are total  milligrams collected.
                                       Ill
-------
                    TABLE  A-12.   WOOD  PRESERVING  TEST  RESUiTS

                                            TEST	CREOSOTE PAN EVAP

                                            TEST DATE	9/25/80	
TEST 3

COMPOUND Acurex I.D. f
80-10-015-
Pentachlorophenol
Phenol
Fluoranthene
Naphthalene
Benzo(a)anthracene
Benzo(a)pyrene
Benzofluoranthenes
Chrysene
Acenaphthylene
Anthracene
Ben;o(ghi)perylene
Fluorene
Phenanthrene
Dibenzofa ,h)anthracene
Indeno(1 ,2,3-cd)pyrene
Pyrene
Benzene
Toluene
Ethyl benzene
Liquid

-52
7.5
31
9.3
10
4.5
0.6
1.4
3.7
0.3
2.8
<0.1
8.9
15
<0.1
0.1
6.7
<0.1
<0.1
<0.1
Pan Bottoms

-53
260
30
599
680
390
91
190
240
840
260
10
660
1100
<10
16
440
6.7
1.4
0.3
Min9

-57
1700
400
32000
24000
20000
500
650
15000
5700
12000
<500
'3COOO
37000
<500
<500
27000
26
2.7
<0.5
XAD

-74
2.8
60
20
2800
1.4
0.25
0.69
1.2
30
70
<0.1
560
200
<0.i
<0.1
13
NA
NA
NA
All  concentrations in units of micrograms per gram except for XAD collections
which are total  milligrams collected.
                                       112
-------
                   TABLE A-12.   WOOD PRESERVING TEST RESULTS

                                            TEST
                                                                    -JEST 3
                                            TEST DATE

COMPOUND Acurex I.D. #
80-10-015-
Pentachlorophenol
Phenol
Fluoranthene
Naphthalene
Benzo (a) anthracene
Benzo(a)pyrene
Benzof 1 uoranthenes
Chrysene
Acenaphthylene
Anthracene
Benzo(ghi)pery";ene
Fluorene
Menanthrene
Dibenzo(a,h)anthracene
Indeno(l ,2,3-cd)pyrene
Pyrene
Benzene
Toluene
Ethyl benzene
Retort 'Drips
-54
1800
<10
200
1400
1000
200
500
850
180
1500
40
2600
2200
20
52
1700
15
<1
<1































































All  concentrations  in  units  of micrcgrams per gram except for XAD collections
which  are  total  milligrams collected.
                                       113
-------
                   TABLE  A-14.   WOOD  PRESERVING  TEST RESULTS

                                            TEST CREOSOTE  PAN   EVAP
TEST
                                            TEST  DATE    9/25/80

COMPOUND Acurex I.D. #
80-10-015-
Pentachlorophenol
Phenol
Fluoranthene
Naphthalene
Benzo (a) anthracene
Benzo(a)pyrene
Benzof 1 uoranthenes
Chrysene
Acenaphthylene
Anthracene
Benzo(ghi)perylene
Fluorene
Phenanthrene
Diben?o(a ,h)a>rithracene
Indeno(l ,2,3-cd)pyrene
Pyrene
Benzene
Toluene
Ethyl benzene
Liquid
-47
0.5
35
6.0
6.4
2.4
C.4
0.3
1.9
0.2
1.4
<0.1
6.0
12
<0.1
<0.1
4.2
3.4
<0.2
0.3
OW Sep Top
-56
8.3
5.2
140
200
60
6.1
15
50
6
56
<10
110
190
<10
<10
100
<0.1
<0.1
<0.1
OU Sep Bot l XAD
-49
1300
800
13000
38000
9200
3COO
500
5400
5700
8000
730
35000
22000
1500
1300
10000
27
0.5
6.8
-68
2.0
<0.4
27
'800
1.5
0.40
1.7
1.1
56
56
<0.4
740
330
<0.4
<0.4
20
NA
NA
NA
All  concentrations  in  units  of micrograms per gram except  for XAD collections
which  are  total milligrams collected.
                                      114
-------
                    TABLE  A-15.   WOOD PRESERVING TEST RESULTS
                                            TEST     PCP  PAN  EVAP
                TEST  1
                                            TEST DATE
9/2?/80

COMPOUND Acurex I.D. #
80-10-015-
Pentachlorophenol
Phenol
Fluoranthene
Naphthalene
Benzo(a)anthracene
Benzo(a)pyrene
Benzof 1 uoranthenes
Chrysene
Acenaphthylene
Anthracene
Benzo(gh1)perylene
Fluorene
Phenanthrene
u1benzo(a ,h)anthracene
Indeno(l,2,3-cd)pyrene
Pyrene
Benzene
Tolusne
Ethyl benzene
Retort Drips

-11
1500
< 10
29
50
60
50
54
50
16
47
< 10
110
150
< 10
< 10
24
< 0.5
< 0.5
< 0.5
OW Sep Top

-12
25000
<10
21
1800
<10
20
20
60
200
240
<10
1500
3000
< 10
< 10
< 10
<0.5
65
41






















XAD

-71
<0.01
<0.01
0.012
0.026
<0.01
<0.01
<0.01
<0.01
0.062
0.012
<0.01
<0.01
0.14
<0.01
<0.01
-------
                   TABLE A-16.  WOOD PRESERVING TEST RESULTS

                                            TEST   PCP   PAN EVAP
            TEST 2
                                            TEST DATE
9/24/80

COMPOUND Acurex I.D. # «
80-10-015-
Pentachlorophenol
Phenol
Fluoranthene
Naphthalene
Benzo(a)anthracene
Benzo(a)pyrene
Benzofluoranthenes
Chrysene
Acenaphthylane
Anthracene
Benzo(ghi)peryler.e
Fluorene
Phenanthrene
Dibenzo(a ,h)anthracene
Indeno(l ,2,3-cd)pyrene
Pyrene
Benzene
Toluene
Ethyl benzene
Liquid 17:15
-25
70
1.2
5.2
0.1
1.6
0.1
<0.1
1.2
0.1
0.4
<0.1
0.3
2.6
<0.1
-------
                   'ABLE A-:V.  '.•> COD FRF'^VII.r.  TEST  RTSUi T5

                                             TEST	PCT_PA^	

                                             TEST  GATE   9/24/30
                                       TEST 2
1
COMPOUND Acure* I.D. «
80-10-015-
Pentachlorophenol
Pheno1
Fluoranthene
Naphthalene
Benzo(a)anthracer.e
Benzo(a)pyrene
Benzoflucranthones
Chrysene
Acenaphthylene
Anthracene
Benzo(ghi)perylene
Fluorene
Phenanthrene
Dibenzo(a,h)anthracene
Indeno(l ,2,3-cd)pyrene
Py.-ene
Benzene
Toluene
Ethyl benzene
J7- id 9; 00

-24
140
0.5
7.9
0.4
3.7
0.1
0.1
3.7
0.1
1.2
< 0.1
1.4
9.5
<0. 1
<0.1
6.1
--0.1
<0.1
<0.1
Fug i live XALi

-73
5.0
1.3
<0.1
3.6
<0.1
<0.1
<0.}
<0.1
0.18
0.03
<0.5
0.2
0.3
<0.5
<0.5
<0.1
NA
NA
NA































i












All  concentrations in units of
which  are  total  mil1igrams col
 rnicrograms per gram except  for  XAD  collections
lected.
                                       117
-------
                      TABLE  A-1S.   WOOD  PRESERVING TE3I  RESULTS

HOOD PRESERVING T££" RESULTS                  TEST	L^LfAN-iVA_p_

                                              TEST DATE    9/25/80
TEST 3
1
COMPOUND Acurex I.D. #
60-10-015-
Pentachlorophenol
Phenol
Fluoranthpne
Naphthalene
Benzo(a)anthracene
Benzo(a)pyrene
Benzofluoranthenes
Chrysene
Acenaphthyleae
Anthracene
Benzo(ghi)perylene
Fluo-ene
Phenanthrene
Dibenzo(a ,h)anthracene
Incteno(1,2,3-cd)pyrene
Pyrene
Benzene
Toluene
Ethyl benzene
"—.,.,.
LiCJ'iD
-37

70
0.4
2.7
0.1
1.4
< 0.1
< 0.1
1.0
0.3
0.4
< 0.1
2.6
2.4
< 0.1
< 0.1
2.0
< 0.2
< 0.2
< 0.2
O.W.^CP TOP
-51

.45,000
<10
2,800
2,000
430
96
320
400
370
1100
7
2400
4000
<10
23
1900
1.2
77
2.3
JO.W. SEP BO
-42

> 980
<10
2,000
220
290
68
190
420
1600
400
< 20
2100
3600
<20
<20
1300
0.2
0.1
1.2
PAN BOTTOMS 1
-35

62
1.2
2.0
1.1
0.5
0.05
0.2
0.4
0.05
0.5
<0.1
1.0
3.5
< 0.1
< 0.1
1.4
<0.2
0.3
<0.2
  All  concentrations  In  units  of micrograms per gram except for XAD collections
  wdich are  total milligrams collected.
                                         113
-------
                   TABLE  A-19.   WOOD PRESERVING TEST RESULTS

                                            TEST   PCP  PAN  EVAP    TEST  3
                                            TEST  DATE
9/25/30
	
COMPOUND Acurex 1.0. #
80-10-015-
Pentachlorophenol
Phenol
Fluoranthene
Naphthalene
Benzo(a)anthracenc
Benzo(a)pyrene
Benzofluoranthenes
Chrysene
Acenaphthylene
Anthracene
Benzo(ghi)perylene
Fluorene
Phenanthrene
D1benzo(a,h)anthracene
Indeno (1,2, 3- cd)pyrene
Pyrene
Benzene
Toluene
1 Ethyl cenzene
"TATf- 	

-69
45
j
0.35
6.8
3.9
0.33
< 0.3
< 0.3
0.34
1.7
3.0
< 0.5
4.0
12
<0.5
<0.5
4.2
NA
NA
NA
Fugitive XAI

-/b
1.7
< 0.01
0.012
1.2
<0.01
<0.01
<0.01
<0.01
0.074
C 019
<0.01
0.30
0.18
<0.10
<0.10
0.01
NA
NA
NA
40X PCP0j?
)C
-Jo
V490,000
<1 ,000
<1,000
< 1,000
<1,000
<1,000
<1,000
<1,000
<1,000
<1,000
<5,000
<1,000
<1,000
<5,000
<5,000
<1,000
<10
12
31
Retort Drips

-43
2100
<10
180
200
80
5.6
26
85
11
55
<5
140
320
<5
<5
140
0.1
0.5
0.5
All concentrations in units of m'crograms  per gram except for XAD collections
which are total milligrams collected.
                                      119
-------
                  TABLE A-20.   WOOD  PRESERVING  TEST  RESULTS


                                            TEST   PCP PAN EVAP
TEST 4



COMPOUND Acurex I.D. #
80-10-015-
Pentachlorophenol
Phenol
Fluoranthene
Naphthalene
Benzo(a)anthracene
Benzo(a)pyrcne
Benzof 1 uoranthener
Chryser.e
Acenaphthylene
Anthrccene
Benzo(ghi)peryle.ie
Fluorene
Pherwnthrene
Diben?.o(* ,h)anthracene
Indeno-1 ,2,3-cd)pyrene
Pyrene
Benzene
Toluene
Ethyl benzene


PCP Working
Soln.
-5R
44000
< 200
430
3800
<100
<100
<]QQ
<100
170
230
<200
1100
1700
<200
<200
350
<1
18
23
TEST DATE

Liquid

-59
41
0.3
1.2
0.3
0.9
<0.1
<0.1
0.7
0.1
0.2
<0.1
1.7
1.5
<0.1
<0.1
0.9
<0.2
0.2
0.2
9/25/80

XAD

-65
2* ,0
420
1400
4700
160
<10
35
150
300
600
<10
1400
12CO
<10
<10
1100
NA
NA
NA


~*
	 1




















All  concentrations  1n  units  of micrograins per gram except fcr XAD collections
which  are total milligrams collected.
                                      120
-------
                TABLE A-21.   WCOO PRESERVING TEST  RESULTS

WOOD PRESERVING TEST RESULTS                  TEST    Plant  D
TEST SITE:
TEST DATE   11/19/30
Field
COMPOUND Acurex I.D. 1
A80-11-043
Description
Pentachlorophenol
Phenol
Fluoranthene
Naphthalene
Benzo(a)anthracene
Benzo(a)pyrer,e
Benzofluoranlhenes
Chrysene
Acenaphthylene
Anthracene
Benzo(ghi )perylene
Fluorene
Phenanthrene
Dibenzo(a.h) anthracene
Indeno(1 ,2,3-cd)pyrene
Pyrene
Benzene
Toluene
Ethyl benzene
116"
-93
Sludge
550
<1.0
3.3
17
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
<1.0
9.3
35
<1.0
<1.0
1.7
NA
NA
NA
121
-104
Sludge
KA














^














r
<0.02
<0.02
<0.02
117
-94
Aeration Ta
2.4
0.2
<0.01 •
0.05
<0.01
<0.01
<0.01
<0.01
0.01
0.01
<0.01
0.03
0.04
<0.01
<0.01
<0.01
NA
NA
NA
120
-103
Tk Aeration T;
HA






























<0.005
<0.005
<0.005
  All concsntratlons in unHs of mlcrograms per  grar except  for XAD collections
  which are total milligrams collected.
                                    121
-------
                             TABLE  A-?l.   Concluded
WOOD PRESERVING TEST RESULTS

TEST SITE:
TEST
Plant D
TEST DftTE 11/19/30
'Field I.D ^ llff j
COMPOUND Acurex I.D. #
A80-11-043
Description
Te"niacntorop:ieno1
Phenol ;.
Fluoranthene
Naphthalene
Benzo(a )anthracene
Benzo(a)pyrene
Benzoflijoranthenes
Chrysene
Acenaphthylene
Anthracene
Benzo(ghi)perylene
Fluorene
Phenanthrene
Dibenzo(a ,h)anthr<)cene
Indeno(l ,2,3-cd)pyrene
Pyrene
Benzene
Toluene
Ethylbenzene
-^
Condenser
32
2.4
1.8
3.2
0.3
<0.1
<0.1
0.3
0.2
0.6
<0.1
1.8
3.7
<0.1
<0.1
1.1
NA
NA
NA
119
-102
Condenser
MA














\














*/
0.02
0.13
0.04
	 1





















|




















  All concentreticns 1n units of micrograms per gram except for XAD  collections
  which are total  milligrams collected.
                                     122
-------
           fll 1C: (4-M
           I a*-i*-* ^-tr a* CLHC tu in
          . c  , ^-w LA«I! N e. ^-e
    (a) Creosote  charge liquid to  pan  evaporator
                 JjUMnJAKjLUiJ^
Figure A- 12.
      (b) Creosote partially  evaporated liquid

Chromatograms from creosote  wastewater  pan  evaporation process.
                        123
-------
                                       JWfl       VcM
          (c)  XAD-2 blank
   rtii C  1.22*9 l-*tLt H t). 4.S i*>*4: A 0 l.fe Prtbti 0 y«.
                                       sows toe 10 2
(d) Creosote  pan evaporator XAD-2



     Figure  A-12.   Concluded
                124
-------
                  :'i
               (a) Penta working soljtion
                         i^t^, a 0 i a
                 (b) Penta retort drips




Figure A-13.  Chromatoqrams of  penta  process  samples,
                          125
-------
             3! I
                 k*'1
                       f
               P.Si
Hi
(c) Penta  oil/water  separator — bottom  layer
    i; te«B n.«; «
    v**Vfi >.«r itf «•>) i; i
    R^MZt &  I,;. .•• i^I
          ll
                         1
  (d) Penta  oil/water separator -- top  layer

           Figure A-13.   Concluded
                      126
-------
              L
                           y> (»« Ci«C IlX 1-X-^Ml Of. 18 IJ

                            LiliULr M «l 4,0 &mi (4 e, '.9 (rfSf i U W. 3
I    i
lk ^'
                           (a) Penta pan  bottoms
                              (b) Penta XAD-2



Figure A-14.   Chromatograms of samples  from penta  evaporation process.
                                   127
-------
                             «*.; iw ro ;2»
  (c) Penta  test  liquid
Figure A-14.   Concluded
           128
-------
                                   APPENDIX  8

                CHAP^CTERIZATIO1,  OF  MULTIMEDIA EMISSIONS FROM
                SPRAY  EVAPORATION  OF  WOOD PRESERVING WASTEWATERS
      Raw data  for  sample  identification and field aata on this  study has
been compiled  and  is  available  upon request.   Copies may be obtained  from EPA
lERL-Ci 26 W.  St.  Clair  Street,  Cincinnati, OH 45268 (513/684-4227).

      This'field  test program  was carried out at plant B and is  described  in
Section 6.

B.I    TEST  SITE

      Table B-l presents a  sunmary of the treated wood production  for the
field  test period.   Figure 3-1  presents a photograph of the pond  in operation.

B.2    FIELD TEST  PROGRAM

      The following  subsections describe the methods and procedures  employed
during sampling.


          TABLE B-l.  TREATED  WOOD PRODUCTION DURING SAMPLING PERIOD
                            Period  11-18-80 to 11-20-80

                                 Creosote        Penta

11-18
11-19
11-20
ni
39
85
40
-
.7
. 3
. 'j

1
3
1
ft3
,403
,013
,432
Tl
77
77
86

.0
.8
.1
f
2
2
3
t3.
,721
,749
,039
                  Total      165.5       5,P,43      240.9     8,509
                       Southern  yellow  pine  —  utility nolcs
                                      129
-------
                                      •

U)
o

                                         Figure B-l.  Photograph of spray pond.
-------
8.2.1   Fugitive t^ission SaTfliruj at the Sorav
       Sampling of fugitive emissions from the spmy pond was conducted using
the concentration profile apparatus (CPA' developed by  the University of
Arkansas,  College of Engineering, Fayettevil ie, Arkansas.  The CPA  as -jsed
during the field test program consists of three devices  and  some  auxiliary
saoport equipment as folios.

Wind velocity profile and direction indicator

       This  device consists of a mast with CUD anemometers positioned at
20 err,, 40  on, 30 cm, 160 cm, 240 cm and 320 cm and a wind direction vane
mounted on top.   Anemometer rotation speed and wine' direction is  transmitted
to appropriate recorders operates by a 12-volt (lead/acid) battery.  The unit
was ootained from C. W.  Thorntwaite Associates (Model 106).  Figure B-2
presents a diagram of the device as assembled for field  use.

Dry bulb temperature device

       This  device consisted of a small  metal cup filled with modeling clay,
centered in  a short section of white PVC pipe to shield  the  clay  from radiant
energy.  These units were mounted on the mast with the cup anemometers using
the same spatial arrangement described for the wind velocity profile mast.
The temperature or the clay was measured periodically using  a hand-held Doric
digital temperature indicator and a small RTD thermocouple.  Figure B-2 also
presents a diagram of the dry bulb temperature devices as they were used in
the field.

Air sampling device

       This  assembly is  not an off-the-shelf item but was designed and
constructed  by the University of Arkansas College of Engineering.  The device
consists of  a 2m mast equipped with holders at six positions for  small
(300 ml) Dewar flasks and U-tubp cryogenic traps.  Tube extenders, upstream of
the traps, allow precise sample heights  to be chosen and maintained.  The
downstream side of U-tube traps are connected to Matheson No. 602 air
rotometers.   Flow was maintained by a portable hand-evacuated vacuum tank which
was modified during the  course of testing to operate from a  Thomas Teflon
diaphragm  vacuum pump.   Figure B-3 presents a diagram of the construction
details for  this device.  Figure B-4 presents a detailed construction view of
the Dewar  flask  bracket  assembly.  Figure B-5 presents a photograph of the CPA
in sampling  position.

       Sampling  fugitive emissions from  the spray ponds was  performed using
the CPA in conjunction with three different sample collection methods.  rhese
included cryogenic U-tube traps, and Tenax and XAD-2 nicroreticular
adsorbents.   in  all  cases the sampled gas/aerosol was routed through a
special ly  irtodi fied midget impinger prior to entry into the appropriate sample
trap.   The midget impingers modified the Smith-Greenburg design by shortening
the impinger stem which  raised the impact.ion plate above the liquid collection
area.   The purpose of this  modification  was to separate and  collect the
                                      131
-------
                               f w\ mj d'. r^ct ion
                            /  "
                     j  '            jJTt
                   4p	^T0'
B-?.  Diagram of wind  velocity profit: and direction indicator
      and di y bulb  temperature devic.
                           13?
-------
Figure 8-3.   Construction details of air sampling device.
                            133
-------
                       F  To  rrnan-.eler
  Upright
  to mast
V Swa'jelor. bulkhead union
           Sample tube
                                                             V Swaaelok
                                                             uni on
Figure E-4.   Detailed construction  view of  the Pewar flask bracket assembly.
                                     134
-------
Figure B-5.  Photograph of CPA in sampling position
                        135
-------
aerosol fraction of  the  sampled  stream,  ultimately  extending  the  effective
sampling time of the cryogenic U-t'jbe  traps  by  limiting  the amount  of
freezable material entering  the  trap.   Figure B-6 presents  a  diagram of  the
modified Smith-Greenburg midget  impinqer.  The  modified  impinners were used  in
conjunction with all three samplina  methods  for the  purpose of  uniformity.

       Cryogenic U-tube  traps were constructed  from  316  stainless steel
tubing, 1/4-inch O.D. 0.020-inch  wall  thickness.  Each tube was packed with
glass beads ranging  in size  from  1.00  to  1.05 mm, purchased from  B. Braun
Melsungen, AKT1ENGESELLSCHAF7, W. Germany.   A small  pyrex glass wool plug was
inserted into each end of the packed U-tubes to retain the  beads.   Figure B-7
presents a diagram of the completed  sampling device.  Prior to  use  in the
field the tubes were cleaned.

       To effect sampling with the cryogenic U-tuhes, the CPA was positioned
at the optimum downwind  location  of  the  spray pond.  The sample devices  then
were affixed to the CPA  at the appropriate heights,  with the  body of the trap
immersed in a liquid oxygen  (LOX) bath.   After  sealing the  sample inlet  end of
the U-tube, a leak test was  perforated  by  apolying at least  10 inches of
Mercury vacuum to the system and  checking the rotometers for  flow indication.
If flow was noted, appropriate measures were taken to correct the leak.

       After completion of a successful  leak check,  the special!v modified
midget impingers were connected and  the actual  sampling was begun.  During the
sampling period, the flow through each sample was maintained  at 100 cc/min by
adjusting the fine flow control valve  mounted at the inlet of the rotometer.
Figure B-8 presents a photograph  of  the cryogenic U-tube sampling device in
sampling position (immersed  in LOX bath).

       The sample trial was  terminated when two or more sample U-tubes became
so restricted with frozen material and it was no longer possible  to maintain
the desired flow rate.

       At the completion of  samplir.g,  the midget impinger and sample U-tubes
were removed from the CPA and sealed.  The U-tubes were placed on dry ice and
maintained under dry ice conditions  for their transport, to  the Mountain  View,
CaMfornia laboratory.  The  modified Smith-Greenburg midget impingers were
analytically rinsed with methylene chloride in  the field laboratory.  All
rinses were collected and stored  in  precleaned  50 ml Wheaton glass  sample
vials with Teflon-lined septum caps.  Rinses with methylene chloride prior to
the next sample run were retained as blank solvent samples for that run.

       The second type of trap for sampling in  conjunction with the CPA
utilized Tenax-GC microreticular  adsorbent resin.  The Tenax traps  were
constructed from 1/4-inch O.D.  2-mm bore ptrex  tubing cut to 4-inch lengths.
Prior to packing with Tenax,  the  tubes were muffled  at 400°C for 4  hrs.  The
tubes w?re  packed with Tenax GC,  80/100 mesh, using a small swatch  of pyrex
glass wool  (also muffled) in each end  to hold the adsorbent in place.  The
tubes were  attached to the CPA with 316 stainless steel  Swagelok nuts and
Teflon  ferrules  to  ensure a  leakfree seal.  Figure B-9 presents a diagram of
the completed  Tenax trap sampling device.
                                      136
-------
                         Swagelok nut
  To sample
  trap
Sample inlet
                                                     12/Srm Sphtricai
                                                     ball joints
                                                Taoer  seal
Figure  B-6.   Diagram  of  modified Smith-Greenburg midget  impinger
                                   137
-------
                              316 Stainless steel
                              swage I ok nut
                           Pyrex glsss wool
6"
                         1.00 to 1.05mm
                         glass bead packing
                                                    316 Stainless steel  tube
                                                    V O.D. x .020" wall
           Figure B-7.  Cryogenic U-tube  construction,
                                   138
-------
Figure B-8.  Photograph of cryogenic U-tube sampling device in Sampling
             position (immersed in LOX).
-------
Teflon ferrolf

316 stainless steel Swage lot  nut
  Pyrex glass wool insert
     Pyrex glass capillary tube

      Tenax GC adsorbent

                                                                 1/4"
                                                                T
    Figure B-9.   Diagram of  Tenax  trap  sampling device.
-------
       Sampling  with  the Tenax traps was conducted in the same manner as
described  for  the  cryogenic  U-tube traps, except the Tenax traps were operated
at ambient temperatures.  Also,  the sampling duration was increased to
approximately  120  min since  the Tenax traps are not prone to flow restrictions
caused  by  a buildup of frozen material.   Figure B-10 presents a photograph of
the Tenax  trap sampling device and Smith-Greenburg midget impinger in sampling
position.

       The XAD-2 sampling device utilized XAD-2 adsorbent resin.  The traps
were constructed from 5-inch lengths of 1/2-inch 0.0. 316 stainless steel
tubing.  Each  end  of  the tubing was fitted with 1/2-inch to 1/4-inch Swagelok
reducing tube  unions  to connect the trap to the CPA.  Prior to packing the
tubes with XAD-2 resin, the  entire unit was muffled at 400°C for 4 hrs.   The
traps were then  packed with  XAD-2 resin, 80/100 mesh, using a small swatch of
pyrex glass wool (also muffled)  inserted in each end to retain the packing.
Figure B-ll presents  a diagram of the completed XAD-2 sampling device.

       Sampling  with  the XAD-2 traps was conducted in the same manner as
described  for  the  Tenax sampling devices.  Figure B-12 presents a photograph
of the XAD-2 sampling device and modified Smith-Gre^nburg Midget Impinger in
sampling position.

B.3    ANALYTICAL  METHODS AND RESULTS

       Samples from the spray pond test site were received on November 25,
1980.  The samples were assigned consecutive laboratory identification numbers
and stored at  4°C  until analyzed.

       Analyses  were  conducted for volatile and semivolatile organics.
Volatile organics  analyses were based on variations to EPA Method 624.
Semivolatile organics (phenols and polynuclear aromatics) analyses were based
on sample  preparation variation to EPA Method 625 in conjunction with fused
silica capillary column GC/MS.

B.3.1  Analysis  of Volatile  Organics

       The analytes of interest were benzene, toluene, and etiiylbenzene.  The
sludge wastewater  and Tenax  trap samples were analyzed for these components.
       A l.Og  aliquot of the mixed sludge was weighed into a 15-ml crimp top
vial.   Pentane (9  ml) and l-brom-2-chlorpropane (10 yg) were added as internal
standards.   A  l-nl aliquot of this diluted sample was injected in a
0.2-percent  Carbowax 1500 on a Carbopack C packed GC column in a Finnegan 1020
GC/MS  instrument.   Analysis and quantitation were conducted per EPA Method 624
using  the  internal standard method.

       Quality control  for the volatiles analysis entailed the analysis of a
method blank and a method standard spiked at 10 yg of sludge.
                                      141
-------
Figure 8-10.  Photograph of Tenax trap sampling device and modified
              Smith-Greenburg midget impinger in sampling position.
-------
-O
O-l
                                                             316  st«inle5?  steel 1/2" O.D. x 0.0.15"
                                                             wall  tubing
                                                            XAD-2  sdsorbent




1

— -J



in
X
/ 1
T 1
..-•:'; ;.. '•;••!•:• ..V-^i •' .:>,:- ;- '::;--:. '\X --^- :-:^- IV i'- :':::^ "-^
X xV


tei
^








1
i _L
±
I/I-." 1/2"
T T
1 t
                                                      316  stainless  steel Swagelok
                                                      1/2" to 1/1" reducing union
                                         Figure B-ll.   Diagram of  XAD-2  trap  sampling device.
-------
Fiqure B-12.  Photograph of XAD-2 sampling device and modi
              Srcith-Greenburg midget impinger in sampling position.
-------
i^ater  Samples

      Water  samples  were analyzed for volatile organics using EPA Method 624
and  1- to  5-ml  samples.   The surrogate compounds d^-benzene and dg-toluene
were added  to  each  sample.

Tenax  Traps

      Traps  were prepared  from Tenax GC (Applied Science) in 1/4 x 4 inch
glass  tubes.   Prior to sampling,  every trap was spiked with dg-benzene
(100 ng)  to  index recovery  of the trapped samples.
      The exposed  Tenax trap contents were transferred to the laboratory in
the  12 x  1/8  inch stainless steel tubes used in the Tekmar LSC2 purge and trap
dev;ce.   The  reassembled traps were purged with helium to remove air and then
thermally desorbed  for analyses per EPA Method 624.

B.3.2  Analysis of  Semivolati1e Organics

      Semivolatile organics analyzed are listed in Table 8-2.  These analyses
were conducted by variations to EPA Method 625 in the sample preparation and
use  of fused  silica capillary colum GC/MS to determine these compounds.


     TABLE  B-2.   SEMIVOLATILE ORGANICS ANALYZED IN  WOOD PRESERVING SAMPLES
                      Compound               Name
                          1          Phenol
                          2          2-Nitrophenol
                          3          2y4,  Dichlorophehol
                          4          2,4,6 Trichlorophenol
                          5          4-Nitrophenol
                          6          4,6-Di.ii tro-0-cresol
                          7          Pentachlorophenol
                          8          Acenaphthene
                          9          Fluoranthene
                         10          Naphthalene
                         11          l,2-Benz(a)anthracene
                         12          Clvysene
                         13          Acenaphthylene
                         14          Phenanthrene
                         15          Fluorene
                         16          Pyrene
                         17          Benzofluoranthenes
                         18          Benzo(a)pyrent
                                       145
-------
Sample Preparation
       The following procedure was ued  to prepare sludge samples:

       1.  Place 10. Oq of the sludqe  in a clean 25D-ml brown bottle.  Add
           10. Oq of anhydrous sodium  sol fate .and 100 ml of pesticide grade
           dichloromethane.  Shake occasionally and allow to sit overnight at
           room temperature.

       2.  Take 1.0 ml of each extract  of GC/FID screening.  Store the
           renaming extract at 4°C.

       3.  As required by the GC/FIO  screening, filter the extract into a
           Kuderna-Danish concentrator  and concentrate to 1.0 ml.

       The GC/FID screening stage was necessary due to the wide variability of
sample concentrations.  Figure 8-13 summarizes the semivolatile extraction
scheme for sludge samples.

       XAD-2 Cartridges

       The XAD-2 cartridge was carefully opened, any silicone stopcock grease
was removed with a Ch^Cl? wetted towel, and the contents transferred to a
preextracted Soxh'et thimble.  The XAD-2 material in the Soxhlet was spike
with surrogate mix and extracted overnight with CH2 Cl;?.  The extract was
concentrated to I to 100 ml based on  the amount of extractable material
present.

       Quality control for XAD-2 samples consisted of the analysis of
surrogate spikes, field blanks, and spiked method blanks.

       Impinqer Catches

       Midget implnger catches were composited for analysis in the
laboratory.  Each composite 
-------
      ICg  sample
    Dry  (Na,SO.)
    and  extract witn
    10  fold CH2C12
    Screen dilute
    extract by
    GC/FID
                         All  peaks
                         in linear
                         GC/I-1S range?
            Greatest peak
            greater than
            500 iig/ml?
     Dilute
     extract  x 100
      Proceed  to FSCC
      analysis
All peaks
less than
10 ,.
      Concentrate
      extract x 100
Figure B-l?   proposed  analysis scheme for phenols/PAH s in
              wood preserving sludges.
                             147
-------
       2.   Adjust the pH of the sample to 12.0 with 6N NaOH.

       3.   Add approximately 30 ml of water and homogenize for a few seconds.
           Add 60 ml of methylene chloride, homogenize briefly again, withdraw
           the homogenizer, and rinse it into the sample with water then with
           5 to 10 ml of methylene chloride.

       4.   Centrifuge the sample aliquot at 1,400 rpm for 5 min to reduce
           formation of an emulsion layer at the water/me'.' vlene chloride
           interface.  Withdraw the extract using a 25-ml Mohr pipet.

       5.   Perform an additional two extractions by adding 60 ml methylene
           chloride, homogenizing, and centrifuging as indicated above.

       6.   Acidify the sample to a pH less t^an 2 using 6N HC1.  Add the acid
           drop-by-drop with constant mixing to prevent foa;..ing.

       7.   Extract the sample again as described in Sections 1.3 to 1.6,
           keeping the addition of water to a minimum.

       8.   Combine and dry the extracts by passing through a drying column
           packed with 10 cm of anhydrous Na2SO^.  Concentrate to a final
           volume of 1 ml using a Kuderna-Danish apparatus equipped with a
           calibrated receiver.

Extract Analysis

       Each of the extracts obtained as described in the previous section was
analyzed for the compounds listed in Table B-2 using fused silica capillary
column GC/MS.  The instrument operating conditions are listed in Table B-3.

       The quality control requirements listed in EPA Method 625 were
followed,  including analytical calibration, mass spectrometer tuning to meet
decafluorotriphenylphosphine (DFTPP) criteria, and the use of the multiple
internal standard quantitation method.  The internal standards used were
dg-naphthalene, d^g-anthracene, and d^-chrysene.

B.3.3  Analytical Results and Discussion

       The qualitative results from the spray pond test program are shown
below.  The sample log which corresponds to this discussion is presented in
Table B-4.

U-tubes

       Samples AS, A10,  A12,  A16, A20, A22, A24, and A7 were analyzed for
volatiles.  Sample A20 contained benzene at 12 ng, toluene at 19 ng, and
ethylbenzene at 9 ng.  All the others were not detected or less than 5 ng was
collected.
                                      148
-------
       TABLE B-3.  FUSED SILICA CAPILLARY COLUMN PARAMETERS
Column:

30m x 0.25m SE-G4 WCOT (JoW Scientific)

Splitless Injection Parameters:

   Injection mode:
   Sweep initiation:
   Sweep flow:
   Column flow (He)
     Measured at
     atmospheric:

Interface:
Splitless
30 sec
+12 ml/min
1.0 ml/min
   Temperature:                         300°C
   Column directly coupled to source (no transfer lines)
Temperature Program

   Initial:
   Program:
   Hold:

Mass Spectral Parameters:

lonization mode/energy:
Total scan time:
Mass range:
30°C for 2 min
Ramp to 300°C at lO°C/min
500°C, 15 min
Electron impact/70 eV
1.0 sec
35 to 475 AMU
                                149
-------
                        TABLE 6-4.  SAMPLE LOG
Sample No.

    1
    2
    3
    4
    5
    6
    7
    1A
    2A
    3A
    4A
    5A
    6A
    7A
    8
    9
   10
   11
   12
   13
   B-l
   B-?
   B-3
   C-l
   C-2
   C-3
   C-4
   C-5
   C-6
   C-7
   C-8
   C-9
    14
    15
    16
    17
    18
    19
    20
    21
    22
    23
    24
    25
    26
Iiiipinqer f\o. IA
Imp inqer No. 2A
I nip inner No. 3 A
Impinqer No. 4A
Impinqer No, 5A
I,T\pinq2r No. 6A
Nell blank
LOX test no. 1, 1335 to 1358, 11-18-SO


Blank U-tube
Impinger No. 1A (XAD-2 B-l)
Impinger No. 2A (Tenax C-l)
Impinger No. 3A (XAD-2 B-2)
Impinger No. 4A (Tenax C-2)
Impinger No. 5A (XAD-2 B-3)
Impinqer fio. 6A (Tenax C-3)

Xad-2 cartridge, Run No. 1, 11-18-80
                1502 to 1717

Tenax Trap, Run No. 1, 11-18-80

(Bottom)

Tenax Trap, Run No. 3, 11-19-8C
(Top)
Impinger rinse 1A
Impinger rinse 2A
Impinaer rinss 3A
Impinger rinse 4A
Impinger rinse 5A
Impinger rinse 6A
Mell blank
Impinger rinse 28
Impinger rinse 2B
Impinger rinse 3B
Impinger rinse 48
Impinger rinse 5B
Impinger rinse 6B
Impinger contents,  test No.  3
11-19-80 (Ter.ax)
11-19-80
Impinger contents,  test No.  3
11-19-80 (Tenax)
                                  150
-------
                        TABLE B-4.  Continued
Sample No.

    A8
    A9
   AID
   All
   A12
   A13
   A14
   A15
   A16
   A17
   A1S
   A19
   27
   28
   29
   30
   31
   32
   33
   34
   35
   36
   37
   38
   B4
   B5
   86
   B7
   B8
   89
   39
   40
   41
   42
   43
   44
   45
  BIO
  Bll
  B12
  B14
  B15
   45
   46
   47
U-tube  (Bottom)
U-tube
U-tube
U-tube
U-tube
U-tube (Top)
U-tube (Bottom)
U-tube
U-tube
U-tube
U-tube
U-tube (Top)
Impinger rinse IB (Bottom)
Impinger rinse 26
Impinger rinse 3B
Impinger rinse 4B
Impinger rinse 513
Impinger rinse 6B (Top)
Impinger rinse IB (Bottom)
Impinger rinse 2B
Impinger rinse 38
Impinger rinse 4B
Impinger rinse 5B
Impinger rinse 68 (Top)
XAD-2~(Bottom)
XAD-2
XAD-2
XAD-2
XAD-2
XAD-2 (Top)
Impinger -inse IB
Impinger rinse 28
Impinger rinse 3B
Impinger rinse 4B
Impinger rinse 5B
Impinger rinse 63
No sample
XAD-2 (Bottom)
XAD-2
XAD-2
XAD-2
XAD-2
Impinger rinse Bl
Impinger rinse B2
Impinger rinse B3
Test No. 4, 11-19-30
1147 to 1317
Test No. 5, 11-19-80
1425 to 1508
Impinger contents,  test No.  5
11-19-80
Impinger contents,  test No.  6
11-19-80
Test No. 6, 11-19-80
1536 to 1645
Impinger contents,  test  No.  7
Test No. 8, 11-20-80
0811 to 1111
Test No. 8, 11-20-80
                                 151
-------
                        TABLE B-4.  Continued
Sample No.

   48
   49
   50
  B16
  617
  B18
  B19
  B20
  B21
  B22
   51
   52
   53
   54
   55
   56
  CIO
  Cll
  C12
  CIS
  C14
  CIS
   57
   58
   59
   60
   61
   62
   63
   64
   65
   66
   67
   68
  C16
  C17
  C18
  C19
  C20
  C21
  C22
  C23
  B26
  B29
 Impinger rinse  B4
 Impinger rinse  B5
 Impinger rinse  B6
 XAD-2~(Top)
 XAD-2  (Bottom)
 XAD-2
 XAD-2
 XAD-2
 XAD-2
 XAD-2  (Top)
 Impinger rinse  IB
 Impinger rinse  28
 Impinger rinse  3B
 Impinger rinse  4B
 Impinger \ inse  5B
 Impinger rinse  6B
 Tenax  Trap (Bottom)
 Tenax  Trap
 Tenax  Trap
 Tenax  Trap
 Tenax  Trap
 Tenax  Trap (Top)
 Impinger rinse  (Bottom)
 Impinger rinse
 Impinger rinse
 Impinger rinse
 Impinger rinse
 Impiger rinse (Top)
 Impinger rinse  (Bottom)
 Impnger rinse
 Impinger rinse
 Impinger rinse
 Impinger rinse
 Impinger rinse  (Top)
 Tenax  Trap (Bottom)
 Tenax  Trap
 Tenax  Trap
 Tenax  Trap
 Tenax  Trap
 Tenax  Trap (Top)
Tenax  blank
Tenax  blank
 XAD-2  blank
 XAC-2  blank
Test No. 9, 11-20-80
1137 to 1237
Test No. 10, 11-20-80
1319 to 1521
Test No. 10, 11-20-80
Test No. 11, 11-20-80
Test No. 11, 11-20-80
1544 to 1744
                                 152
-------
                        TABLE 6-4.  Concluded
Sample No.
  100
  101
  102
  103
  104
  105
  106
  107
  108
  109
  110
  111
  112
2 x 113
2 x 114
2 x 115
  116
  117
  118
  119
  120
  121
2 x 122
2 x 123
     Sample Log — Wastewater and Sludge

Pond sludge 11-2-30 (0830)
Pond sludge 11-2-80 (0330)
Pond sludge 11-2-80 (0830)
Pond wastewater (pump discharge) 11-2-80 (0830)
Pond wastewater (pump discharge) 11-2-80 (0830)
Pond wastewater (pump discharge) 11-2-80 (0830)
Sludge spray pond 11-19-80 (1215)
Pond grab sample (surface) 11-19-80 (1015)
Pond wastewater (pump discharge) 11-19-80 (1045)
Pond sludge (5 ft from edge 11-19-80 (1215)
Farmers pond (bottom core sample) 11-19-30  (1000)
Farmers pond (behind RR tracks)  11-19-80 (0145)
Farmers field (3-part core soil  sample) 11-19-80  (1050)
Farmers ponr1 VOA
Pond VOA (pump discharge) 11-19-80 (1045)
Pond VOA (surface water) 11-20-80 (0820)
Floe tank sludge to drying bed — 1-19-80 Plant  0
Aeration tank afer floe tank —  1-19-80 Plant 0
Condenser pond before Hoc tank  — 1-19-80  Plant  D
Condenser pond VOA Plant D
Aeration tank VOA Plant D
Sludge VOA Plant D
Wastewater from separator 11-20-80 (0930) PCP
Wastewater before pond 11-20-80  (0910)
                                  153
-------
       Samples A9, All, A13, A19,  Al,  A6,  A21,  A23,  and A25 were analyzed for
phenols and polynuclear aromatics.   All  results  except for the following were
negative.  The detection  limit was  1  ug  collected  for  all samples.

       Sample                    A9              All        A\_

       Pentachlorophenol         41              5.2        4.0

       Fluoranthene                1.4            1          1

       Pyrene                      1.1            1          1

       Phenanthrene                1.7            1          1


       Figure B-I4 is  a representative chromatogram  from a U-tube extract.

XAD Cartridges

       Samples Bl, B2, B3,  B5, B7,  B9, [ill,  B14, B16,  B18T 820, B22, 826, and
B29 were extracted and analyzed  for  phenols  and  polynuclear aromatics.  No
compounds were detected to  a detection limit  of  1  ug.  The detection limit for
naphthalene in these samples is  10  ug  due  to  a  minor contamination of the
XAD-2.  Figures B-15 and  B-16 compare  the  chromatograms from an XAD-2 blank
and a sample.

Tenax Traps

       All  Tenax traps Cl through  C23  were analyzed  for benzene, toluene, and
ethylbenzene.  These compounds were  not  detected in  any samples.  Due to a low
level of Tenax contamination, the  detection  limits were 0.7 ug for each of
these compounds.

Waters, Sludges, and Soils

       These samples were analyzed  for volatile  aromatics, phenols, and
polynuclear aromatics  as  listed  in Tables  B-5 and  B-6.  Figure B-17 is a
typical chromatogram for  a  volatiles analysis.   Figure C-18 is a ch-omotogram
for a pond  sludge extract.

       The  comoosite pond water  sample (Field I.D. 103+104+105 and lab I.D.
80-11-043-83) was also analyzed  for  oil  ano grease by standard methods.  The
measured value was 160 yg/1.

Impinger Catches

       Impinger catch samples were composited as follows:

       «   Sample 1 - Sample 6

       ii   Sample 7 + Sample 20
                                      154
-------
            RIC                                           DATA: BNA43I4 HI
            91/88/81  15s 16:98                              CfiLIt C810381B HI
            SAMPLE: 680-11-043-14 A-2 IU=TOTAL FU=.5 HJL=28NG 03,10,12
            RANGE: G    1,2200  LABEL: N  0,  4.0  QUAN:  A 0, 1.0  BASE: U 20,   3
SCANS  100 TO 2290
RIC
                                                                                                   1662970.
>s — , •- '

H ft .
k H J\ MUK
500 innn ic,oo 2000
&:2C' lb:JO 25:00 2 3: 20
                                                                                                     SCAU
                                                                                                     TIME
                 Figure  8-14.   Total ion current chromatogram U-tube extract.
-------
                             RIC
                             81/19/81  15:29:68
                             SftflPLE: A88-1(-843-34 69 !UL=2WG 08, IP, 12
                             RANGE:  G    1,2208  LABEL:  N  8, 4.8  GHJAN:
       DATA:  BHA4334 HI
       CAL1:  ('.0110316 t)2

ft  0,  1.8  EASE: U 20,   3
                                                                                                       SCANS  188 TO 2200
               i80.e-
                                                                                                                      2015230.
                 RIC
en
en
                                 U
                                      8:20
                                                            IbHO
                                                                                                                        •Tf M(J
                                                                                                                        TTTF
                                                 Figure B-15.    Chrornatogram from  XAD-2  sample.
-------
    RIC
    81/12/81 17:55:09
                                                   DATA: BHA43<7B *1
                                                   CfU.1: Cfill2PlA «3
SCftNS  100 TO 2208
         SAKPLE:  AS0-11-643-47 B2b BLANK 1UL=20NG 08,18,12
         RANGE: G  1,2298  LABEL: H  fl. 4.0  QCW: A 8, 1.8
                                                      BASE: U 20,  3
RIC
                                                                                       875529.
WjyL4ii
                                                        'II      I
                                                        .'1 ^L'-.^.^
                 500
                 8:20
                               IF.: 4'1
                                                                                    TIME
                    Figure  B-16.  Chronatogram from an XAD-2  blank.
                                            157
-------
                                       TABLE  8-5.
HOOD PRESERVING TEST RESULTS

TEST SITE:	
TEST   Spray Pond Samples

TEST DATE

COMPOUND Acurex I.D. *
A80-11-043
Description
Tentacnloropneno i
Phenol ,
Fluoranthene
Naphthalene
Ben?o(a)anthracene
Benzo(a)pyrene
Benzofluoranthenes
Chrysene
Acenaphthylene
Anthracene
Benzo(ghi)perylene
Fluorene
Phenanthrene
Dibenzo(a,h)anthracene
Indenc(l ,2,3-cd)pyrenc
Pyrene
Benzene
Toluene
Ethyl benzene
00-102+109
-80
_omposite i-.luc
5,000
<50
5800
1500
2600
20
87
2000
230
1700
67
5600
9000
<50
85
4400
NA
NA
NA
103-105
-83
qe Comp.Wat
15
<0.1
3.0
4.0
0.4
<0.1
0.1
0.6
0.1
0.7
<0.1
1.7
6.4
<0.1
<0.1
1.6
NA
NA
NA
107
-87
2r Pond Wat
2.2
<0.1
5.7
6.3
1.4
0.1
0.5
1.6
0.3
1.6
<0.1
3.7
12
<0.1
<0.1
2.9
NA
NA
NA
108
-88
r Pond At Purm
16
<0.1
2.7
2.3
4.5
<0.1
0.1
6.2
0.1
0.7
<0.1
2.C
7.4
<0.1
<0.1
1.1
NA
NA
NA
 All concentrations  1n  units  of micrograms per gram except for XAD collections
 which are tot.al milligrams collected.

                                          158
-------
                                      TABLE 8-6.
HQODJRESERVING TEST RESULTS

TEST SITE:AUbJna-
T E S T

TEST DATE
Field I.D.
COMPOUND Acurex I.D. *
AEO-11-043
Descri Dtion
PentAclrt6rop1.enc>1
Phenol ..
Fluoranthene
N-iphthalene
Benzo(a)anthracene
Benzo(a)pyrene
Benzofluoranthenes
Chrysene
Acenaphthylene
Anthracene
Benzo(ghi)perylene
Fluorene
Phenanthrene
Dibenzo(a ,h)anthracene
Indeno( 1 , 2 , 3- cd ) pyrene
Pyrene
Benzene
Toluene
Ethyl benzene
122

-97
Vastewater
790
17
41
• 66
<10
<10
<10
<10
<10
<10
<10
58
24
<10
<10
21
NA
NA
NA
123

-98
Wastcwater
1160
48
23
120
<10
<10
<10
<10
<10
17
<10
22
67
<10
<10
15
NA
NA
NA
114

-100
Spray Pond
NA















0.015
<0.005
<0.005
its

-101
Pond Pump
NA















0.015
0.040
<0.005
 All concentrations ''n units of micrograms  per gram except for XAD collections
 which are total milligrams collected.
                                         159
-------
PIC
12/29/81
Sample:  Pond VOA N0115
Range G  1,600
«   I
   i ..I
                                  .  Internal
                                  "i— standard
     Figure 8-17.   Volatile analysis  chromatogram.
                                                                €0*
                              160
-------
           RIC                                            CATA: D
           01/M/fli 12:23:89                               CALI: i>3114olH tt
           SAfPLE: Ai-e-lt-*W3-S« OUPL.OF^IO 1UL=2(WG D3,U3,12
               :  G   t,2280  LA6£L: M  8, 4.0  CHjMtC. A  0,  1.6  Pft^E: 0 W,   3
                                   SCwttS  !feJ TO 220?
RIC

                                      /i
                                 i*
                                 ill!  i
                                 |'f  '
M;
                                                              M
                                        l:»)
                                                                          ,
                                                                          fl
                                                                          U,,"»
                                                                                    Il'C'O
            ^igure B-18.   Total  ion  current trace of  pond  sludge extract,
                                                                                                  C/H,"
                                               161
-------
       «   Sample 8 - Sample  13

       •   Sample 14   Sample  19

       •   Sample 21 - Sample  26

tlacr of these composite samples was  concentrated  and analyzed for phenols  and
semi vola ti les.   No compounds were  measured  at  the detection limit rif 1  iiq.
Figure 8-19 is  a chromacrcgram of  a  typical  irr.pinger extract.
                                       162
-------
iee.c-i
              RIC                                            DATA: BNA3125  #1136
              81/13/Sl 15:58:69                               cftLI: C911381A »3
              bftfVLE: ASS-11-643-125 COUP AHAL PRCCI FU=0.5«L 1UL=26HG 03,13.12
              RANGE: G   \>Z2*Q LABEL: H  9,  4.6  QWlN: A  0,  1.8  BASE:  U 20,  3
SCANS  169 TO 22C8
 RIC
                                                                                                      7S672,
                                                 j
                      WO
                                            1008
                                            IbHO
                                                                                                       TIMi:
               Figure  B-19.   Typical  chromatogram of  ar. impinger  extract.
                                                 163
-------
                                   APPENDIX C

          CHARACTERIZATION OF EMISSIONS AND RESIDUES FROM THE DISPOSAL
               OF WOOD PRESERVING WASTES IN NONFOSSIL FUEL BOILER
       The handwritten raw data for this study has been compiled and is
available upon request.  That data covers preliminary and isokinetic source
emission sampling, total n.ydrocarbon determination, and specific
low-molecular- weight hydrocaroon determinations.  Copies may be obtained from
EPA-IERL-Ci L'6 W. St. Clair Street, Cincinnati, OH  45268 (513/681-4227).

       The scope of this program focused on the gaseous emissions discharged
from the stack, and the ash streams which result during combustion and
pollution control.

       Material balance estimates were difficult since ash and fuel  flowrates
were not metered by the operator.  Estimates were made of each s'ream and the
appropriate material balance evaluation of the destruction and removal
efficiency performed (See Section 7).

C-i.   TEST SITE

       Table C-l presents a summary of ti.e total production during the field
test period.

         TABLE C-l.  SUMMARY OF TREATED WOOD PRODUCTION FOR THE PERIOD
                     JULY 21 THROUGH JULY 25, 1980
Treatment
Product
Penta P^nta Fire
heavy oil light oil Creosote CCA* retardant**
m3 ft3 m3 ft3 m3 ft3 m3 ft3 m3 ft3
Utility Poles 255 7962 76.8 2712 1.0 37
Pil ings
Lumber
Plywood
30.8 10S8 199 7044 11.3 400
12.5 440 52.7 1860 49.6 1753 186 6583 48. C 1717
27.2 962
  CM    Copper chromate arsenate (waterborne)
  Waterborne  formulation
                                      164
-------
C.2    FIELD TEST PROGRAM

       The sampling program and collection matrix  is presented in section 7
and Table 7-1.  The following subsections describe the equipment and
techniques employed during sampling.

C.2.1  Preliminary Measurements

       Preliminary gas characteristics were determined using EPA Methods 1
through 4 (Federal Register, Volume 42, No. 160, August 18, 1977).  Using
these criteria, tne required number of sampling points was established.  With
the boiler operating under normal  load conditions, two traverses were
conducted at ricnt angles to one  another on the south stack (No. 2).
Figure C-l presents a schematic of the stack cross section and traverse point
locations.  Gas velocity measurements were taken ucing a calibrated 6-ft
S-type pitot tube connected to a  0- to 1-inch Magnehelic Series 200 gauge
manufactured by Dwyer Instruments Company, Michigan City, Indiana.  Exit gas
temperatures were measured using  a Chromel-Alumel  (Type K) thermocouple and a
diaital thermal indicator manufactured by Doric Incorporated.  Table C-Z
presents a summary of the velocity/temperature profile data.


    TABLE C-2.  SENARY OF VELOCITY/TEMPERATURE PROFILE DATA FOR SOUTH STACK
                     South port                        East port
AP \
Lv. -cion cm
1 .99
2 1.30
3 1.40
4 1.50
5 1.55
6 1.65
7 1.63
8 1.63
9 1.52
10 1.35
-1,0
inches
0.39
0.51
0.55
0.59
0.61
0.65
0.64
0.64
0.60
0.53
Temperature
C° F°
120
131
141
163
16o
174
175
177
178
180
248
268
286
325
335
345
347
351
353
355
AP f
cm
1.42
1.09
1.37
1.52
1.65
1.80
1.88
1.90
1.88
1.73
inches
0.56
0.43
0.54
0.60
0.65
0.71
0.74
0.75
0.74
0.68
Temperature
C° F°
142
142
159
174
131
180'
182
is:3
184
184
290
290
319
346
357
3f5
359
362
363
364
                                      165
-------
                                  Sampling  Locations
                Traverse Point  Number
                South  Port  East  Port
                    1
                    2
                    3
                    4
                    5
                    6
                    7
                    8
                    9
                   10
11
12
13
14
15
16
17
IB
19
20
                                                  Location fron Inside Stack Wall
 2-7/6
 4-3/16
 6-3/4
10-1/4
19-3/4
23-3/16
25-5/8
27-1/2
29-3/16
                                           Norti
                ports
                                                               t   5
                                                              3D"
                              _L
                                j
Figure C-l.   Schematic cf  traverse  point  locations,  south  stack,  no. ?.
                                         166
-------
       Preliminary gas moisture content was calculated using nolychrcmetric
data.   Successive moisture values, as determined during t.ne actual test runs,
then were used to update the preliminary calculated values.  Exit gas
molecular weight was c'ternined by standard orsat analysis before and after
each test run.  The ra-' data collected  in the field are not presented in this
report,  but can be obtained as described above.

C.2.2  Isokinetic Source Sampling of Boiler Flue Gas

       Sampling of high-rnolecular-weight organic emissions from the outlet
stack was performed using the EPA Method 5 isokinetic sampling train as shown
in Figure C-2.  The train consists of an in-stack filter, a heated glass-lined
probe, an XAD-2 polymer sorbent trap and impingers.  The  first impinger, a
modified Greenburg-Smith (without an impaction plate), was empty, followed by
an XAD-2 polymer sorbent trap and a Greenburg-Smith impinger charged with
100 ml of 30-percent hydrogen peroxide.  The third  impinger was also an empty
modified Greenbjrg-Smith, followed by a silicon dioxide drying trap to protect
the vacuum pump and sampling module from moisture.  Figure C-3 presents a
photograph of the sampling train  in sampling position on  the south stack.

       For each isokinetic source test, a sample was drawn from the fan outlet
(at a predetermined constant velocity point) through a probe fitted with the
appropriately sized nozzle.  Four complete sets of  samples were collected.
All sampling was conducted during normal boiler operation.  Table C-3 presents
a summary of the pertinent isokinetic source test parameters.

       At the completion of source sampling, the sample train and probes were
transported to a field laboratory.  Samples were transferred from the sample
trains to specially cleaned and labeled storage containers.  The probe nozzle,
probe, and connecting lines were  cleaned also and recovered samples were
transferred t^ the appropriate storage  containers.  Immediately following
sample recovery, all samples were iced  in the field and maintained under those
conditions during transport to the analytical laboratory.

C.2.3  Total Hydrocarbon Determination  of Boiler Flue Gas

       A Moael 400 total hydrocarbon analyzer (THC) manufactured by Beckman
Instruments of Fuil3rton, California, was used to continuously monitor total
hydrocarbons in the sampled gas stream  at the south stack.  This analyzer uses
the flame ionization detection (FID) method.  The analyzer output was recorded
using a Model 58^ strip chart recorder  manufactured by Linear Instruments
Corporation, Irvine, California.

       The FID was operated using zero  grade 1.0 hydrogen fuel and zero grade
air supplied by Airco Industrial  Gases, Santa Clara, California.  Hydrogen
fuel and zero air pressure were set at  207 kPa (30  psi) and 104 kPs (15 psi),
respectively, usinn internal differential pressure  regulators in the analyzer.

       Sampling was conducted using the system shown in Figure C-4.  The g=
-------
                Heated Teflon sampling li

                            I
                                                                    XAD-2 trap
Dry gas meter control module
                                               Empty

                            Gas meter thermocouples
                                                       Tine adjustment
                                                       byoass valve
                                                                                      Ice/water
                                                                                      bath
                                                                                Impinger
                                                                                thermor.oi.p1e

                                                                                    SiOj trap
                                                                                Vacuum line

                                                                          Vacuum gsge
                                                                             I
                                                                    Coarse adjustmpnt valve

                                                         Airtight  vacuum pump  j
Orifice
Hagneheltc
Gage
                                Dry  test meter
                                                                          J
         Figure  C-2.   5chematic diagram  of  an  XAD-2 iiigh-ir.olecular-weight
                         nass particulate sampling train.
                                            168
-------
          ^^•^^•H^^UBMMHI^Bi^BH^HH
Figure  C-3.  Modified  EPA Method 5  sampling train  in  sampling position
              on south  stack.

                                     169
-------
                           7y->  sintered  stainless  steel filter

                           r
— O.OW in stainless steel  probe

    	•*»-  To stack
                    Tnree-*ay stainless steel solenoid valve


                   ^eat traced Teflon sample line (30.46m)
£
1 	 Teflon
~s .
n
J?
* / / f~ /
^. f


diaphragrr vacuum pump



.' / / .f j' .r J* ,' y ,r
^ 7 s ' s - -'-*'„/,-•',-





7 .' t

' b
\


\A *4j 2 ml injection
MJ lYI— 1 -OOP and


L.
J

Unburned




hydrocarbon
analyzer
(FJD)


Strip
chart
recorder




<
rv
k.
«3

O
u
tJ














M <
rf


0>
3
*-
CS;
3_













L
up

^X C
bacKl


Ctrorr.atOOT'arh
I
1
r ; L/.

Strip
Chart
recorder



M <





























k.
^

o
u.
1L
^-,



H











H C
i£


C
3
^~
(\
a




i 	


r— 1
(^







l>
C
L,
L

LJ
g_i
X
ush vaU-r







<
n



^H







    CalIbration
    gases
Figure C-4,   Schematic  of  unburned  hydrocargon  and  gas clu-omatograph
               saiTpling  system.
-------
TABLE C-3.  SUMMARY OF ISOKINETIC SOURCE TEST PARAMETERS
Test
no.
)
2
1
4
Pate
7/23/80
7/23/80
7/?1/90
7/?5/80
Test period
(24-hr clock)
1000-1600
0850-1450
0850-1450
0800-1350
Sample
time
(min)
360
350
360
350
Barometric
pressure
(inches Hg)
30.57
30.00
30.69
30.75
Sample
volume
(scf)
12.79
17.34
25.81
30.64
Average
stack gas
temp (°f)
318.9
331.1
312.0
367.4
Molecular
weight
(Ib/lb mole dry)
29.29
29.28
29.43
29.37
Percent
moisture
12
7.?
5.0
7.9
Percent
1sot< inetic
98
100.4
100
105.3
-------
Ohio.  The filter removed fine participates which,  if  allowed  to pass  into the
THC analyzer, c^.uld ucclude the FID sample  inlet capillary.  A 0.006m  O.D.
stainless steel probe connected the filter  unit to  the heated  sampling  line
via a th.-'ee-way stainless steel solenoid valve.  This  valve  allowed the
introduction of sample gas or calioration gas depending on which mode  of
operation was desired.  A 12.2m, heated-traced, 0.01m  O.D. Teflon sample line
manufactured by Technical Heaters, Inc. of  San Fernando, California, was used
to transport, the sample to the vacuum  p'jmp.  Sample  line temperature
controllers were supplied by the manufacturer.  A Teflon-coated diaphragm,
vacuum pump IP vuf actured oy Thomas Industries of Sheboygan,  Wisconsin, was
used to pull •. >° sample through the lines.  From the gas vacuum pump exit, the
sample was split and routed to the analyzers via short lengths of heated
Teflon line.

       Prior to operation and calibration,  the completed sampling system was
operated at approximately 297°K above  normal sampling  and calibration
conditions, and was purged for several hours with zero nitrogen to remove any
traces of residual  hydrocarbon contamination in the  lines.   During this
"bake-out" procedure, stainless steel  tube  unions, filters,  and probes were
heated using a propane torch.  Before  and after each test, a leak test was
performed on the sampling system, followed  by calibration of the THC analyzer
using zero nitrogen (<0.5 HC) and a mixture of 535 ppm methune in nitrogen.
During calibration, the three-way valve was positioned to block the sample
probe and filter, allowing the calibration  gas to pass into  the heat-traced
sample line.  Introducing the calibration gases at this location ensured the
sample gases and calibrations gases were treated in  the same manner,
nullifying possible undesirable effects due to absorption or wall loss in the
sampling line and system.

C.2-4  Specific Low-Molecular-Weight Hydrocarbon Determination of Flue Gas

       Periodically, benzene, toluene, and  ethylbenzene concentrations were
determined in the boiler flue gas.  Small portions of  the sampled gas routed
to the total hydrocarbon monitoring system  was diverted and  injected into a
Varian Model 3700 gas chrematograph (GC) fitted with an FID.  Figure C-4
depicts the sampling system.   Using a  sample valve fitted with a 2-cm3
injection loop, the sample was injected into a 6-ft x  1/8-in O.D. stainless
steel column packed with I percent SP100 on Carbopack  (80/100) mesh.

       Calibration  standards  for the compounds of interest were prepared
onsite using a  501  Teflon bag and the methods outlined in "Evaluation of
Emission Test Methods for Kalogenated Hydrocarbons," (Vol. I, EPA-600/
4-79-025, March 1979).   Table C-4 presents  the results of the analysis and a
chronology of sampling/injection time  during the field testing period.

       Resultant chromatographs indicate that the components of interest were
not detected at concentrations less than 0.1 ppm in  the sampled gas.  These
data  are in close agreement with previously presented data for the total
hydrocarbon analysis.
                                      172
-------
       TABLE  C-4.   SUGARY  OF  SPECIFIC  LOW  MOLECULAR WEIGHT HYDROCARBONS
                   HETERMiNAT IONS  OE  FLUE GAS
Date
7-21-80
7-22-30



7-23-80








7-24-80








7-25-80








Time
1623
1044
10r->5
1110
1548
0944
1100
1304
1319
1336
1342
1349
1426
1507
1040
1113
1130
1240
1215
1400
1415
1430
1449
0323
0845
0913
0940
100C
1015
1125
1201
1206
Procedure
Injection calibration standards
Inject flue gas sample
Inject flue qas samole
In ect zero gas
Inject flue gas sample
Inject flue gas sample
Inject flue gas sample
In ect flue gas sample
Inject flue gas sample
In ect calibration standards
Inject flue gas sample
In ect flue gas sample
Inject flue gas sample
In ect flue gas sample
Inject calibration standard
Inject calibration standard
Inject calibration standard
Inject flue gas sample
Inject zero qas
In ect calibration standard
Inject calibration standard
Inject calibration standard
Inject flue gas sample
In ect calibration standard
Inject calioratior. standard
In ect flue gas sample
Inject zero qas
In ect flue gas sample
Inject C}-Cg calibration standard
Inject Ci-i,'g calibration standard
In ect flue yas sainple
Inject flue qas sample
Results*
—
<0.1 ppm
<0.1 ppm
—
—
<0.01 ppm
<0.01 opm
<0.01 ppm
<0.01 ppm
	
<0.0l ppm
<0.01 ppm
<0.01 ppm
<0.01 ppm
	
—
—
<0.1 ppm
—
—
—
—
<0.01 ppm
__
—
<0.01 ppm
—
<0.01 ppm
—
—
<0.01 ppm
<0.01 ppm
Concentration  of sought components
                                      173
-------
C.2.5  Composite Sampling

       Composite samples of the rrulticone hopper ash, boiler  bottom ash,
wooawaste fuel, and sludge/wastewater wore collected during the field  sampling
period.  Sampling at these locations was performed  at approximate  1-hr
intervals during each test run.  Samples were  obtained  by collecting  and
transferring equal bulk aliquocs of the material into precleaned sampl?
storage containers.  Figure 7-1 shows the locations of  each sampling  location.

C.2.6  Grab Sampling

       Grab samples of  tne baghouse hcpper ash, pre-processing bulk penta  in
heavy aromatic treating oil,  and bulk creosote were collected during  the field
sampling.  Bughouse No. 2 hopper ash samples were  collected at the end of  each
test run when  the hoppers were  emptied.  Grab  samples of  the  penta and
creosote treating formulations  were supplied by plant personnel.

C.3    ANALYTICAL METHODS AND RESULTS

       Samples from the boiler  test site were  recei ^d  on July 29, 1980.   The
samples were assigned corrective laboratory  identif 'cation numbers and stored
at 4°C until analyzed.

C.3.1  Analytical Methods

       Analyses were conducted  for  volatile  organics, semivolati le organics
 and  metals.  Volatile organics  analyses  were based on variations  to EPA
Method 62'1.  Semwolatile organics  (phenols  and polynuclear  arornatics)
 analyses were  based on  sample preparation variations  to EPA Method 625  in
conjunction with  fused  silica capillary  column GC/MS.   Metals analyses were
conducted  using standard  atomic absorption  techniques.

Analysis of Volatile Organics —
       The analytes of  interest were benzene,  toluene,  and ethylbenzene.   Only
 the  sludge samples were analyzed tor these  components.

       A l.Og  aliquot of  the  mixed  sludge was  weighed  into a  15-ml crimp  top
 vial.  Pentane (9 ml) and l-bromo-2-chloropropane  (10 pg) were added  as
 internal ctandards.  A  1-ul  aliquot of  this  deluted sample was injected  in a
 0.2-percent Carbowax 1500 on  a  Carbopack  C  packed  gas GC in a Finnegan 1020
 GC/MS  instrument.  Analysis  and q-janti tat ion were  conducted per  EPA Method 524
 using  the  internal standard  method.

       Quality control  for  the  volatiles  analyses  entailed the analyses  of a
 method blank, and  a method stanaard  spiked  at 10 ng/g  of sludge.
 Analysis of Semivoiatile  Organics

       Semivolatile organics  analyzed  are  Msted  in Table C-5.   These analyses
 were conducted by v riations  to EPA Method  625 in  the  sample preparation  and
 the  use of fused  silicon  capillary  column GC/MS to determine these compounds.
                                       174
-------
TABLE C-S.  SEMIVOLATILE ORGA'JICS ANALYSED  III V.'OOD PRESERVING SAMPLES
             Compound Number              Compound Name
                    I                     Phenol



                    2                     2-Nitrophenol



                    3                     2,4 Dichloropheho:



                    4                     2,4,6 Trichlorophenol



                    5                     4-Nitrophenol



                    6                     4,6-Dinitro-o-cresol



                    7                     Penta



                    8                     Acenaphthene



                    9                     Fluoranthene



                   10                     Napthalene



                   li                     Benz(a)anthracene



                   12                     Chrysene



                   13                     Acenaphthylene



                   14                     Phenanthrene



                   15                     Fluorene



                   16                     Pyrent



                   17                     Anthracene
                                 175
-------
Sample Preparation —
       The sludge sampler were prepared as follows:

       1.  Place 10. Og of the sludge  in * clean 250-ml browf buttle,  f-
           10. Oq of anhydrous sodium  si:1, at.? and 100 ml of pesticide grade
           dichloro^lhane.  Shack occassional ly ano allow to sit overnight ct
           room  .cmperatiir 2.

       2.  Take 1.0 ml of each extract for GC/FIO  screening.  Stan the
           remaining ext'Ll2 weticd towel, and the contents transferred to a
preextracted coxhlet thimble.  The XAO-2 material  in the Soxhlet was spikcc'
with surrogate mix and extracted overnight with CH^CI^-  The e/tract was
concentrated to 1 to 100 ml based on  the amount of extractable material
prssent.

       Quality control for XAD-2 samples consisted of the analysis  of
surrogate spiK°s, field blanks and spiked method h!o'ks.

Ash Samples—-
       20. Og of tne flyash were placed in a clean  Soxhlet thimble,  then spkt-d
with surrogates at concentrations i saniple /^as extracted »vHh
CH^C^ overnight and concentrated to  1.0 ml.   Puality control for ash
samples consisted of the use of surrogate spikes and the analysis of a iiethod
blank and a spiked sample.

Extract Analysis —
       Each of the extracts obtained  as described  in the previous sections
were analyzed for the compounds listed in Table C-5 using fused silica
capillary column GC/MS.  The instrumental operating conditions are  listed in
Tuble C-6.
       The quality control requirements listed in ^PA Method 625
followed, including analytical calibration, mass spectrometer tuning to meet
decaf luorotuphe-nylphospline (DFT?P) criteria, and the use of ti;
-------
  ICg sample
Dry (Ni-,50.)
and extract with
10 fold CH2C12
Screen dilute
extract by
GC/FID
                     All peaks
                     in linear
                     GC/MS range?
      Proceed to FSCC
      analysis
        Greatest peak
        greater than
        500 ug/ml?
 Dilute
 extract x 100
All peats
less than
      Concentrate
      extract x 100
 Figure C-5.   Analysis  scheme  for  ohenols/PAH  s  in wood
              preserving  sludqos.
                          177
-------
      TABLE  C-6.   FUSED SILICA CAPILLARY COLU: N PARAMETERS
Column:

     30-n x 0.2£m SE-54 KCOT (J & W Scientific)

Splitless Injection Parameters:

     Injection node:                Splitless
     Sweep initiation:              30 sec
     Sweep flow:                    >12 ml/min
     Colu-nn flow (He)
       measured at
       atmospheric:                 1.0 ml/min

Interface:

     Temperature:                   100°C
            directly coupled to source (no transfer lines)

            Progra.T,:

     Initial:                       30°C for 2 min
     Program:                       Ranp to 300°C o 10°C/min
     Hold:                          300°C, 15 min

Mass Spectral Parameters:

     lonization mode/energy:        Electron impact/70 eV
     Totoal scan time:              1.0 sec
     Mass range:                    35 to 475 AMU
                              178
-------
C.3.2  Results and Discussion

       The quantitative results for tiie testi'.ci during wood  ana vjaste
incineration are given in Tables C--7 to C-9.  Day 1 samples  were not analyzed.

Volatile Organics—
       Low Tevels of volatile aromatic hydrocarbons k-.ere detected in croescte
vFigure C-6).  These levels are greatly reduced in the waste sludge.  The
total hydrocarbon content of the stack gas was  0.01 ppm.

       The detected levels of aromatic Hydrocarbon? in the sludge samples were
close to the detection Unit.  The reported levels have been corrected for
(rethod blank contribution.  The accuracy of the method at these low nar.ogram
levels is poor.  Since the injection of organic extracts on  the volatilos GC
column led to the accumulation of hiqher-molecular-weigrit aromatics.  It was
necessary to back out the column at 200°C after every few analyses.

Semivo". at i le Organics

       The application of fused silica capillary column GC/MS to this project
allowed for greatly improved compound identification over that obtainable with
packed column methods.  Polynuclear aromatic isomers such as
phenanthrene/anthracene and benzo(a)anthracer>,e/chrys3ne can  be resolved by
this method.  But the Finnegan 4000 capillary injection system is subject to a
nigh degree of front-to-back discrimination.  In the split/splitless mcde of
injection, the sample first is volatilized in the injection  port then
reconden~>ed at the head of the column.  This process results in a substantial
variation from injection to injection in the fraction of a given component in
the sample placed on the column.  An extra degree of random  error is
introduced into the determination of early eluting compounds (phenol and
naphthalene) by decreasing the precision of the analysis.  To correct for this
effect, the early elutinq compound quantitations were corrected using the
recovery of the surrogate spike, dg-naphthalene.

       Figure C-7 is a chromatogram from the analysis of semivolatile organics
in a sludge sample.  The major identified peaks are labelled.  There are
clearly a large number of organics present in addition to those of  interest to
this program.  Figure C-8 is a chromatogram from a bottom ash extract.  Only
the polynuclear aromatics were detected in ash samples; no phenols were
detected.

       Penta and 2-nitrophenol were detected at low but significant levels
only in the samples from days 2 and 3.  There is no simple explanation of the
nitrophenol:  this compound was never detected in a sludge or ash sample.
Figures C-9 and C-10 are cnromatograms of the day 3 XAD-2 cartridge extract
and an XAO-2 blank cartridge, respectively.  They should be  contrasted with C7
and 8.

Metals

       The results of the metals analyses are shown in Table C-10.
                                      179
-------
                 TABLE C-7.  ANALYTICAL RESULTS FOR TEST PAY 2
Compound
7-^itrophfenol
Penta
Pnenol
F luoranthene
Naphthalene
8enzo(a)anthracene
Eenzo(a)pyrene
fenzof luoranthene***
Chrysene
Achenaphthy lene
Anthracene
Benzo'ghijperylene
Fluorene
Phenanthrene
D i benzo I a, n) anthracene
Indeno(l,2,3-cd)pyrene
Pyrene
Benzene
Toluene
Ethylbenzene
Botto-i
ash-
<0.5
<0.5
<0.1
92
10
7.6
1.4
9.3
1.2
4.4
4.5
<0.5
0.6
24
<0.5
<0.5
29
NA****
NA
NA
Baqhouse
ash"
<1.0
<1.0
<0.f;
0.7
10
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<1.0
<0.5
6.9
<1.0
<1.0
<0.5
NA
NA
NA
Mechanical
hopper ash*
<0.5
<0.5
<0.1
.0.5
10
<0.1
<0.1
<0.i
<0.1
<0.1
<0.1
<0.5
<0.1
0.6
<0.5
<0.5
<0.1
NA
NA
NA
Lludge*
<10
740
1200
2200
1300
160
<20
52
180
120
760
<20
1200
1800
-------
                      C-3.  ANALYTICAL RESULTS  r'03  TEbT DAY 3
Cc,.,<
2-Nitrophenol
Penta
Pheno'
Ftuoraitnene
Naphthalene
Benzo(a)anthracene
Benzo(a)pyrene
Benzof luoranthene***
Chrysene
Acheniphthylene
Anthracene
Ben:o(ghi)perylene
Fluorene
Phenanthrene
Dibenzo(d,h) anthracene
Incteno (1,2, 3-cd ) py r ene
Pyrene
Benzene
Toluene
Ethyl benzene
Bolter,
ash*
<0.5
<0.5
<0.8
15
18
0.6
0.1
0.9
0.7
3.0
1.0
cO.5
' 0.8
31
<0.5
<0.5
7.9
NA***»
NA
NA
Baqhojse
ash*
<1.0
<1.0
<0.2
0.2
3.9
<0.2
<0.2
<0.2
<0.2
<0.2
<0.2
<1.0
<0.2
3.0
<1.0
<1.0
<0.3
NA
NA
NA
Mechanic al
hopper ash*
<0.5
<0.5
<0.1
0.6
6.5
<0.1
<0. 1
<0 . 1
<0. 1
<0.1
<0. 1
<0.5
<0.1
0.5
<0.5
<0.5
<0.1
NA
NA
NA
Sludge
<10
260
1000
340
1000
120
<30
64
120
68
250
<20
420
590
<20
<20
310
<1.
3.
5.
* XAD**
74
}?0
<2
3
1100
<1
<5
<5
<1
<1
<1
<5
<1
<1
-------
                       c-9.  A:,ALYTICAL RESULTS FOR  TEST  DAY  4
Compound
2-Nit-opnenol
Penta
Phenol
Fluorantheie
Kap^thilene
Benzo(a)3nthracene
Ben:o(a)nyrep-e
Benzof luoranthene***
Chrysene
Achen^.phthylene
Anthracene
Benzo(ghi)perylene
Fluorene
Phenaothrene
Di ben*o ( a, h) anthracene
Indeno(l,2,3-cd}pyrene
Pyrene
Benzene
Toluene
Ethylbenzene
Bottc-n
ash*
<0.5
<0.5
<0.6
1.4
9.6
<0.1
<0.1
<0.1
<0.1
<0.1
0.?.
<0.5
<0.1
3.0
<0.5
:0.5
0.4
fiA****
NA
NA.
Baghouse
ash*
<1.0
<1.0
<0.3
6.2
5.1
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<2.5
<0.5
7.3
<2.5
<2.5
<0.5
NA
NA
NA
Mechanical
hopper a^h*
<0.5
<7.4
<0.1
1.7
2.2
<0.1
<0.1
<0.1
0.3
<0.1
0.2
<0.5
<0.1
0.4
<0.5
<0.5
<0.4
NA
NA
NA
Sludge*
-------
 RIC                                            DATfl: U0274S II
 e9'ie/88 2ei39:eo                               c^u: i^swee si
 SA«PVEi V8274 UOA 1LI  INJ
 RfiNGEi C   I, 358  lft8EU N  8,  4.8  QUANi A  6.  1.8  Bf)cEi  U  20,  3
49
                                                                                                     SCWS    1 TO  558
                                                                                                                    468592.
CO
co
                RIC
                                                                                       Peak ?60 --  Internal  standard
                               Cont.am
                                                                                                         5C9
                                                                                                            4-CHpCH, + Cont.
                                    3:15
                          289
                          6:39
9:43
16:15
                                                                                                                     SCAN
                                  Figure  C-6.   Volatiles  analysis  of diluted  creosote.
-------
RIC
CO
          IW.IH
                                                                 DATA) upeeia *i
                              I2il3i88                            CflCh Cai589A 13
                             wwis.er-wr-zr s.     «.SJL-I»<: 010
                            c   i.2eo9 ueat N  e.  4.e  QU.WJ A e. i.a BASE: u 20.  3
                                                   921
                                                                                         scons  iee TO
            RIC
388

CD
224
!










, >






9 '
3 i
i !
10
439 8



f
1
;
!
(
1 '
' i
'
:
Si
!• 1
H '
!ki
rtlll I
u
JM
5-




j
h

s!

I
1 \







\
3


616






1







Si

, • '
111

791












L
a
V*l
$:?9



7










1
M
3J^tJOO


J130 Peaki niriberpd «s per











*
1936







^,






!
ill
table C-B
1









Sil
6









jfr.LiT,.^ IW ,ra
	 1 	 1 	 t—- i 	 1 	 *- T ' T ' T 1
lf>» IV*} 2W0 SCAM
1^:41} r*'!'X> 5:'<:2rt T!If£
                           Figure C-7.   Toral  ion current  chromatogram of waste sludge  extract.
-------
RIC
fa l.2»»
       N e. «.e
                                                       OSTAt MP771I »I
                                                       CW.lt COTI9"Wi «3
                                                   i; 018
                                                A  e. j.o  BASEI u M.  3
                                                                               SCONS  :«» TO
               10
                     522
             14
             973
                              715
                         354
                    A
Ail
                                   OT9

                     9
                     ner
                                            959

                                            'UN
                                                     16
                                           16:48
                                                            I.T53
                                                                         1555        !914
                                       IW3
                                       23:00
                                                                             SC&S
                                                                        3;::20 Tint
           Figure C-8.   Total  ion current chromatogram of  bottom  ash extract.
-------
RIC
99x22^6?  19:22:98
SflMPLEi 67-627-41 B)fH* 8.5UL-I8NC 010
RANCH) C   l,?90e Lfieei: H  6,  4.0  OUCH:
      416
                                                                        OftTA: UP2741
                                                                        CAL1:
                                                                     9, 1.8  BASE: U
                                                                                    tl
                                                                                      13
                                                                                                  SCANS  see TO
              PIC
CD
O1
                      2P6
                                                                                                                 .76154 4.
                                   10
•VJ
268
1
i-JLv-JJ
j
/
,i


^.Ji
534

ll

594
U.

712 .
,.ll 1 I. I
                                                              1023
                                       liei    1757
                                                                                 H22
                                                                                                             2056  SCAN
                                                                                                             33:20 TIME
                              Figure  C-9.   Total  ion current  chromatogram  of an  XAD-2 extract.
-------
oo
•—i
            I98.6-,
              RIC
                      21«

                                «29
                                    we
                                                                            HP22R il
                                                                            Ce91590«  13
                                                      Oie,D8. 027-838, XAO BLftW, BH»fl.FV=2.0M
                                                 H 8, 4.e  OUflH: ft  e, I.e  BrtSE: U 20,  3
saws  iee TO 2eee
                                                 783
                                                                                   1317
               123904.
                                                           16:-!*)
                   Figure C-10.   Total ion  current chromatogram from an XAD-2 blank cartridge.
-------
                                         TABLE C-10.  METALS  ANALYSIS
CD
CO


Bottom ash day 2
BsUcm ash day 3
Bottom ash day *
Baghowse ash day 2
Baghouse ash day 3
Bagnouse ash day 4
Med. hopp«r Bh day 2
Hed. Kopp
-------
C.4    LABORATORY A ANALYTICAL RESULTS

C.4.1  Analytical Methodology
A.
Extraction and Cleanup Procedures
       The se-'en samples received for analysis include three different sample
types.  Sludge and Penta in Oil may be  treated as one type of sample, ash is a
second type, and the blank is  a third sample type.  Each of these types of
samples required different procedures for extracting the CDDs and COFs.
However, the subsequent steps  involved  in cleanup of the sample extracts, as
well as the mass spectrometric procedures employed to quantitate the compounds
of interest were common to all samples.  The three sample extraction methods
are outlined below, followed by a description of the methods common to all
samples.
       1.  Sludge and Penta in Oil Samples

       a.  Place an accurately weighed  aliquot (typically Ig) of the sample in
           a clean flint glass bottle (Teflon-lined screw cap).   Add the
           internal standard solution (225 yl of benzene containing 25 ng
           37Cl4-2,3,7,8-TCDD  and 200 ng 37Ci4_i^,3,4,6,7,8-HpCDD)
           add 40 ml of hexane, and agitate to dissolve the sample.

Proceed as outlined in the steps common to all samples listed below.

       2.  Ash Samples

       a.  Place an accurately weighed  aliquot (typically Ig) of the ash into
           a glass extraction  thimble,  add the internal standard solution
           (225 ul benzene containing 25 ng 37Cl4~2,3,7 ,8-TCDD and 200 ng
           37Cl4-l,2,3,4,6,7,8-HpCDD) to t.ie sample, and place the thimble
           in a Soxhlet extractor.

       b.  Extract the sample  for 16 hours using ber.zene as the extraction
           solvent.

       c.  Concentrate the extract to about 0.5 ml in a stream of prepurified
           nitrogen while heating the sample at 55° in a water bath.

       d.  Quantitatively transfer (using hexane as the transfer solvent) the
           concentrate to a clean 125 ml flint glass bottle (Teflon-lined
           screw cap), and add additional hexane, so that a total of 40 ml
           hexar.e is present in the bottle.

Proceed with the steps common  to all samples listed below.
       3.  Blank Sample

       a.  Place the  internal standard solution into the bottle (225
           benzene containing 25 ng 37Cl4-2,3,7,8-TCDD and 200 ng
           37ci4-l,2,3,4,6,7,8-HpCDD).
                                                                 of
                                      169
-------
       L.   Add aboat 200 ml  of hexane to tne bottle and agitate for 5
           minutes.   Quantitatively transfer uit: hex an .J extract to  a clean  125
           ml  flint  glass bottle (Teflon-lined c-cre.v  crp)  and rinse the blank
           bottle with sufficient hexane to obtain a  fi-idl  volume of 40 ml  of
           hexane and combine all hexane ext.-acts in  the 125  ml flint g^ss
           bottle.

Proceed as  outlined  in the steps common to all samples  listed below.

       4,   Cleanup Procedures Applied to all Sc^ples

       a.   Extract the organic solution with 50 ml of 20 percent  (w/v)
           potassium hydroxide by agitating fur 10 minutes.   Allow  for
           complete  separation of aqueous and organic layers  and  remove
           aqueous base (bottom) layer to base waste  bottle.

       b.   Extract the organic solution with 50 ml of doubly  distilled  water
           by agitating the sample for 2 minutes.  Allcuf time for complete
           layer separation and discard the aqueous (bottom)  l^yer.

       c.   Extract the organic solution with 50 ml of concentrated  su'ifuric
           acid (cautiously adding sulfuric acid) by  agitating the  sample for
           15 minutes.  Allow for complete layer separation  and discard acid
           (bottom)  layer into acid waste bottle.

       d.   Repeat Step 3 until acid layer is nearly transparent.

       e.   Extract the organic solution with 50 ml of doubly  distilled  water
           by agitating for 2 minutes.  Allow for complete  separation and
           remove aqueous (bottom) layer.

       f.   Dry the organic layer over sodium sulfate  and then quantitatively
           transfer  a portion of the organic layer to a clean test  tube and
           reduce the volume to incipient dryness using a stream of
           prepurified nitrogen ana while maintaining the test tube in  a 55°
           water bath.

       g.   Fabricate a glass Macro-column (20 mm OD x ?10 mm  long)  tapered  to
           6 mm 00 on one end.  Pack the column with  1.0 g  silica,  2.0  g
           silica containing 33 percent (w/w) IM NaOH,  1.0  g  silica, 4.0 g
           silica containing 44 percent (w/w) concentrated,  sulfuric acid and
           2.0 g silica.  Quantitatively transfer tne residue obtained  in
           Step f to the column with 45 ml hexane. Collect  the eluent  and
           concentrate to 1  to 2 ml in a centrifuge tube.

       h.   Construct a disposable liquid chromatoqrapny column as follows.
           Cut off a Pyrex 5 ml disposable pipet at the 2 ml  mark and use the
           lower portion of  the pipet.  Pack the satiU  end  with a plug  of
           silanized glass wool.  Next add 1 oram of  Woelm  basic  alumina
           previously activated overniaht fit i?00°C in a muffle furnace  and
           placed in a dessicator for 30 minutes just prior  to use.
                                      190
-------
i.   Using a disposable pipet, transfer the sample onto the liquid
    chr (joa to graph y co 1 urn .

j.   Rinse the centrif joe tube with 2 consecutive 0.3 ml portions of ?
    percent CH^Cl? in hexane, and transfer the rinses  to the
    alumina column.
k.  Eiute tiie column witn 10 ml of 3 percent (v/v) CH^Cl? in h
    ana uiscard the eluent  (taking care not to let the column run dry).

1.  Elute the column with 15 rr,l of 50 percent (v/v) CrbC^ 'n
    hexane ard retain the eluent for analysis.

m.  Concentrate the solution to approximately 1 ml, using a stream of
    prepurified nitrogen as before.  Rin^e the centrifuge tube wall
    with an additional 1 ml of CHjCl? and reconcentrate.

n.  Quantitatively transfer the residue (using methylene chloride) to
    two 2 .TI! micro-reaction vessels (one-half of the residue in each
    vessel).  Tne contents of one vessel are used for CDF
    determinations and the contents of  the other vessel for CDDs.

o.  Evaporate the solution  in each of the micro-reaction vessel almost
    to cr/r.ess as previously, rinse the walls of each vessel with
    approximately 0.5 ml CH^C^, and evaporate contents just to
    dryness.

p.  Approximately 1 nour oefore GC/Kb (GC/LRMS or GC/HRMS) analysis,
    dilute the residue in the micro-reaction vessel with benzene to the
    required amount.  Gently swirl benzene on portion of vessel to
    ensure dissolution of the dioxins.

q.  If upon preliminary GC/MS analysis  the sample appears to contain
    interferences, high performance liquid chromatographic clean-up of
    the extract is accomplished at this point prior to further GC/MS
    analysis.  For HPLC, a Varian Model 5021 instrument is employed
    equipped with a DuPont Zorbax-OOS (C-18, reverse phase) column.
    See below for further HPLC details.

Gas Chromatograph y/Mass Spectrome tr y Procedures

a.  Parameters for Gas Chromatographic-High Resolution Mass
    Spectrwictric (GC-HRMS) Analysis of the Extracts.
    Instrumentation:  Varian 3740 Gas Chromatoqraph coupled through an
                      AE I silicone mpmbrane separator to a modified AEI
                      MS- 30 Mass Spectrometer.  Modifications to the
                      MS- 30 include changes in the ESA power supoly to
                      permit inclusion  of a custom built, step-scan
                      circuit which is  driven by a Nicolet 1074 Signal
                      Averaging Computer,  Four masses are rapidly
                      scanned at t'i<; retention time of the diovin or
                      furan of interest.
                               191
-------
Coaaitions for t h_o_Cji' s Cnrc.nat o 
-------
               Ionizing Voltage:  70 eV

               Accelerating Voltage:  4 KV

C.     High Performance Liquid Chromatography Procedures

       a.  Parameters for high performance liquid chromatographic (HPLC)
           clean-up of the extracts:

           Instrumentation:  Varian Model 5021 Microprocessor Controlled  High
                             Performance Chromatograph equipped with CDS-llIl
                             Data System

           Parameters:

               Pressure:  Minimum:   10 atm
                          Maximum:  250 atm

               Injection Loop:  25 yl

               Column:  Guard:  35 v Vydac SC Reverse Phase
                                4.0 cm x 0.4 DTI I.D.

               Analytical:      2-DuPont Zcrbax-ODS
                                25.0 cm x 0.6 cm I.D.

               Temperature:  Guard Column:  Ambient
                             Analytical Column:  50°C

               Detector:     Fixed UV:  254 nm, 0.01 A.U.F.S.

               Variachrom UV-Vis:  TCDD, 235 nm, 0.01 A.U.F.S.
                                   HxCDD, HpCDD, 245 nm, 0.01 A.U.F.S.
               Program:  Time^

                           .0

                           .0

                           .0

                           .1

                         20.0
Code
A
Flow
Event
Event
Event
Value
100 Methanol
2.5 ml/min
Hold
Inject
Reset
                                      193
-------
  TABLE  C-ll.   LIST OF ION MASSES MONITORED USING GC-SELECTED-ION
                 MONITORING MASS  SPFCTROMETRY FOR S'VJJLTANEOUS
                 DETERMINATION  OF MNO-,  DI-, 1RI-, TETRA-,  PENTA-,  HEXA-
                 HEPTA-, AND OCFA-CHLORINATED DIt!ENZQ-p-DIOXINS AND
                 OIBENZOFURAf.S
Class of S'uaber of Monitored n/z for
Chlorinated Chlorine Dib«r_iof uract
Diber^odioxin Substitueata Cl2H?-xC'C:^s
or C!ber.:of-jran (X)
Mono- 1 202.019*
204.016
Di- 2 235.980*
237.977
Tri- 3 269.941*
271.938
Tetra- 4 303.902*
305.899
Peuta- 5 337.863*
339.860
Hexa- 6 373.821
375.818
Eepca- 7 407.782
409.779
Octa- 8 441.743
443.740
Monitored o/z for >
Dibenzo-p'dioxins 1
C12«8-«°ZCI* '
<
218.013s
220.011
251. 974°
253.972
285.940*
287.937
319.897*
321.894
327.885b
256.933
1258.930'
353.858*
355.855
389.816
391.813
423.777
425.774
431. 7651"
457.738
459.735
>pproxlraate
rheoreticsl Kitlo
ixpected on Easi*
sf Isotonlcr Abundance
1.00
0.35
1.00
0.69
0.99
1.00
0.74
1.00
0.21
0.20
0.57
1.00
1.00
0.87
1.00
1.00
0.86
1. 00
"•Molecular ioo peak.

t'37Cl4-labelled BpCDD standard peak.

c'Ions which csn be monitored in TOD  analyses for confirmation purposes.
                                    194
-------
TABLE C-J2.  SEQUENCE OF OPERATIONS IN GC/MS (MS-25) ANALYSES 0^
             CHLOROOIBENZODIOXINS AND CHLORODIBENZOFIJRANS IN FIRST
             INJECTION OF SAMPLE EXTRACT

ELAPSED
TIMK
(HIM)
0.00
1.50
2.00
4.50
5.00





8.00
8.75
9.50





16.00
16.75




25.00
28.00
45.00






60.00
95.00



rVKNT
ln)pctton, uplitlcaa
Turn on apllt valve
Begin temp prof ran to 220*C
Open coluon flow to Maaf Spec.
Start PROGRAM '1
Sweep " 100 pprt
fine on each nu«* • 0. 1 5 tec



Colnan re»ch
-------
        TABLE C-13.   SEQUENCE  OF OPERATIONS  IN  GC/MS (MS-?5)  ANALYSES OF
                        CHLORODIBE'iFOOlOXlNS  AN!.) CHLOUODIflENZOFURANS IN  SECOND
                        INJECT 10',' OF  SAMPLE EXTRACT
ELAPSED
 0.00
 1.50
 2.
 4.50
 6.trO
 6.00

fl.OO
12.75
24.00
25.00
Zi.OO
45.00
46.00
60.00
70.00
90.00
95.00
           RVKNT

Injection,  aplltlees
Turn co ^f'llt  vjilve
Bef.In te&p  prograra  to 2JO*C
Open flow to M.ni9 Spec.
Start PKOCRAM  it
  Swrep ™ llx)  ppa
  Tl&e on ejch mass " 0,15 eec

Coiuar. rtr on -rtcli WIBO - 0.55  sec
          Stop PROCKAM #8
          Return to Initial tcrap
                                         CC
                                         COLUMN'
                                         TEMPEKATURK.

                                           190*C

                                           19n°c
                                           202'C
                                           210*C
                                            220*C

                                            220*C
                                            220*C
                                            22fi*C
                                            220*C
                                            225'C
                                            235*c
                                            235'C
                                            235'C
                                            235*C
                                            235'C
                                                      TEMPERATURE
                                                      KKOCRAH
                                                      RATE
                                                      (A'C/HIN)
                                                         5'C/raln
                                                         5*C/mln
                                                          5'C/mln
                                                          5°C/Din

IONS


MONITORED BY
HASS
(m/z






















SPECTROMETER
)
235.980
237.977
251.974
253.972
303.902
305. R99
319. R97
321.894
327.885
373.821
375.818
389. S16
391.813
407.782
409.779
423.777
425.774
431 765
441.743
443.740
457.738
459.735
COMPOUNDS
MONITORED
Cl2 fi'rans
Cl2 furanj
Cl2 dloxlna
Cl2 dloxlns
Cl^ furans
C&4 furane
Cl4 dloxlna
C>4 dloxlna
3?C1 labelled TCDD
Clf, furena
Clfc furans
Cl(, dloxlns
Clfc dloxlns
Cl? furans
Cl? furena
Cl? dloxlns
Cl; dtoxlna
37C1 labelled TCDD
Clg furans
Clg furans
Clg dloxlns
Clg dloxlns
                                              195
-------
C.4.2   Results  and  Discussion

       As  indicated in the procedural GC.'MS discussion presented in the
previous  pages,  two separate gas chromatographic-mass spectromotric methods of
analysis  were  enp'oyed in this program, one utilizing low resolution gas
chromatography-high resolution mass spectrcmetry (LRGC-HRMS), and the"other
utilizing  high  resolution gas chromatography-low resolution mass spectrometry
(HRGC-LRMS).   Fur determination of total TCDDs in the extracts of the Camples
LRGC-HRMS  was  emp'oyed.   This technique yields essentially unequivocal
quantitative results for the total TCCOs present in the analyte, but does not
yield  information regarding the specific TCDD isomers which are present.  The
results obtained with this method for the samples are listed in Table C-14.
Both ni/z  320  and m/z 322 (these are nominal masses, actual m/z's monitored
were 319.8966  and 321.8936) were monitored as indicators of TCDD during the
period when TCDDs elute  from the gas chromatograph and thus, quantitation of
the TCDDs  detected  can be based upon the signal observed at either mass.  The
theoretical »~atio of m/z 320:m/z 322 resulting from TCDD (based on the known
isotropic  abundances of  35ci and 37rj ancj the numbers of Cl substituents
in the molecular ion) is 0.77, and as can be seen from the data, si-ice the
TCDD valuer, calculated from th^ response at each ion mass are reasonably
consistent, the experimentally observed ratio is essentially the same as the
theoretical ratio.   This is another criterion which the data should satisfy in
order  to  certify with confidence that TCDD is indeed detected.  Since the mass
at rn/z 327.8846, which arises from the 37Cl4-2,3,7,8~TCDD internal
standard  added  to all samples prior  to processing, was monitored concurrently
with the  two masses typical of native TCDDs, and the quantitation of native
TCDDs  is  actually based  upon the ratios of the signals at m/z 320 and m/z 322
to that at m/z  328, the  values listed in Table C-14 are inherently "recovery
corrected."  This is, of course, one of the chief reasons for utilizing an
internal  standard,  and results in improved accuracy.  The percent recovery of
the internal  standard is listed solely for the purpose of illustrating the
overall  efficiency  of the analytical procedure.  Clearly, the recoveries are
generally quite high and the procedures are, therefore, acceptable for
analyses  of these samples.

       For determnino the concentrations of each of the various classes
(monochlorinated through octachlorinated) of chlorinated dibenzo-p-dioxins and
dibenzofurans  in the sample extracts a sophisticated HRGC-LRMS technique was
employed.  As  indicated  in the previous section, a complex computer-controlled
multiple  ion monitoring  scheme was employed.  The compounds in each extract
were quantitated during  two separate GC/MS analyses.  The chromatographic and
mass spectrometric  conditions employed and the ions monitored during the two
GC/MS  analyses  were given previously in Tables C-12 and 13.  These conditions
permit m/z's  typical of  each class of the CDDs and CDFs to be monitored during
the appropriate time interval corresponding to the gas chromatographic
retention  time  interval  for the various members of a given class.  As
expected,  the monochlorinated CDDs and monochlorinated CDFs have similar
retention  times.   However, use of the 50 M (WCOT) fused silica column provides
optimum separation  and minimized overlap of individual compounds.  It must be
noted  that of  the 75 possible CDDs and 135 possible CDFs, authentic standards
of only a  limited number were available for use in calibration.  Most of the
                                      197
-------
                      TABLE  C-14.  LOW  RESOLUTION GAS CHROMATOGRAPHIC-HIGH  RESOLUTION MASS
                                    SPECTHHMETRIC ANALYTICAL  RESULTS FOR AfUREX SAMPLES
WSU SAMPLE NO
ACC-11
ACC-12
ACC-13
ACC-14
ACC-15
ACC-16
ACC-17
AOIREX SAMPLE NO.
80-07-02''-3
80-07-027-26
80-07-027-26(29)
80-07-027-43
80-07-027-44
80-07-027-44(45)
blank. Empty Bottle
TOTAL TCDD DETECTED
•/i 320 B/Z 322 AVERAGE H.D.C. ng/a
1.1 ppb
0
0
3.7 ppb
0.9 ppb
3.3 ppb
0
1.10 ppb
0
0
3.4 ppb
0.6 ppb
3.3 ppb
0
l.li ppb
0
0
3.4 ppb
0.8 ppb
3.3 ppb
0
0.5
0.2
0.9
0.2
0.2
0.2
0.3
PERCENT
RECOVER**'
121
108
1
24
126
85
135
93
oo
                 ••Biiad on
an internal itandtcd prior to «aapl« ptoccoslng.
-------
CDO arid CDi-  peaks observed in the analyses of the sample extracts cannot be
assigned to a specific isorer.  Thus, in arriving at a quantitative value for
a given class of COOs or CDFs, the areas of the mass chromatographic peaks
appearing at the appropriate retention times, and having the appropriate mass
spectral response, were sunanea and compared to the corresponding area observed
from injection of a known quantity of a calibration standard of the same
class.   In general, a single CDO or CDF isomer of each chlorinated group
(i.e.  monochlor inated, diclilor inated, etc.1) was used in the calibration
process.  Mass chromato grams were obtained in the course of the complete GC-MS
scans resulting from two injections of a mixture of such COO and CDF
standards.  The CDO and COF isomers used in obtaining this caliuration data
were 1-chlorodibenzo-p-dioxin; 2,7-dichlorodibenzo-p-dioxin;
1.2,4-tricnlorodibenzo-p-d-ioxin; 2,3,7 ,8-tetrachlorodibenzo-p-dioxin;
3'Cl4-2,3,7,8-tetracnlorodibenzo-p-diox.in;
1,2,3,4,7v8-hexachlorodibenzo-p-dioxin;
1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin, octachlorodibenzo-p-dioxin;
2,4-dichlorodibenzofuran; 1,2,4-trichlorodibenzofuran;
2,3,7,8-pentachlorodibenzofuran; 1,2,4 ,5 ,6 ,7 ,9-hexachlorodibenzofuran; and
octachlorodibenzofuran.

       Mass  chromatograms resulting from the full GC/MS scan of two injections
of Acurex Sample 80-07-027-43 for all classes of CDDs and COFs are shown in
Figures C-ll through 28.  The concentrations of COOs and CDFs in all the
Acurex samples analyzed, determined from similar GC/MS data, are presented in
Section 8.

       In the case of the TCQDs, the HRGC-LRMS system was employed to
partially elucidate the identity of the specific TCDD isomers present in each
of the sample extracts orginally found by LRGC-HRMS to contain TCDDs.
Figure C-28  shows the mass chromatograms resulting t'r  ; injection of s
calibration  standard containing 12 separate TCDD isomers, as well as the
37Cl4-2,3,7,8-TCDD internal standard.  Figure C-28 snows the result of
analyzing another calibration mixture containing only 5 isomers and the
37Cl4-2,3,7,8-TCDO internal standard.  Finally in Figures C-29 and 30
HRGC-LRMS results for two of the Acurex samples are shown.  As can be seen in
Figure C-30  this sample extract apparently contains 4 TCDD isomers (ar well as
the 3^Cl4-2,3,7,8-TCDD internal  standard).   However, some of these peaks
may be representative of more than one isomer.  In fact, some of these peaks
are rather broad, suggesting that other isomers may indeed be present.
Notewofthy is the fact that the 2,3,7,8-isomer is clearly absent in this
sample  extract.   Finally,  as shewn in Figure C-30, five or possibly six TCDD
isomsrs are  apparently present in sample a.80-07-027-44(45).  Here again some
of the  discrete  peaks may represent multiple isomers.  The results displayed
in Figure 4  suggest that only a trace of the 2,3,7,8-TCDD isomer may be
present in  this  sample.  A summary list of stanoards used by this laboratory
Is given in  Table C-15.

C.5    LABORATORY B ANALYSIS

       laboratory E received five samples  for CDD and COF analysis.  As these
samples required extensive cleanup procedures, they are listed separately.
                                      193
-------
            204-285
                                                                   38
  >,00   0.19   0,33  9:58   1,18   1.38  1,58   2,18   2,33   2,59  3:19
   i i i i i r i i I i i i ii i i , i I i n i i ii i i I i I i i i i i I ll 1 I i I I I I 1 1 I I II I i i I I , Ii i II i i ii i I i I i i i M i i I i ii i . i ' I ll I ,. i i i i i ,
         18     29     30
                                171 1 H |T . M 1 1 .Tp-nn 1 1 1 1 1 1 n 1 1 111 1 1 1 1 1 1 1 1 1 1 H 1 1 ' i ri-n-r,
                             40     30     60    70      80     30     108
Figure  C-ll.   Results  of HRGC-MS  analysis of  ash  sample 80-07-43
               for monochlordibenzofurans.
                                200
-------
4i^-jv  uRUsa SL.HN KtHUKl/  KUh,  fl C C 1 3 C B 0 8 1

* 218-219  t  220-221
108
 00   0,18  9,38   0,58   1,18   1,38  1,58   2,18   2,38   ?, 59   3,19

	I I I I I I Illl I I I Illtl I II I I ll I III I I I ll I I I I I I mini i I i . ii I	i , , , I i , , , jini)i.iij_ii t.ilr I I I I I . 1 I
        1 1 i [ 1 1 in 1 1 1 1 1 1 1 1 n n 1 1 1 1 n i M 1 1 ij i : 1 1 1 1 1 1 1 1 1 ll I M
          13     20     38     40    50     60     78
                                                           83     90     100
 Figure  C-12.   Results of HRGC-MS analysis of ash  sample 80-07-027-43
                 for monochlorodibenzo-p-dioxins.
                                    201
-------
  -30  WHO oS  3 I, ft N K t P U R T >  RUN. OCC120002


  235-236   « 237-238
180
   8,00   6,38  1,18   1,56  2,38   3, '9   3,39   4,39   3,13   5,59
 70
 50
 28
     160*-5629
     160V. = 3564
                                       \J\J

                                                      , M I , I, I I I I t I
     nun i q 11 111 ii 11 111 in ni i[ i; i in 1111. 11 n 11 M[: nil 1111 [ 11 n 1111111 n 1111 M |i IM 111 n j in M 11

         23     «9    63     f)8     180    120    140    166    180   280
Figure C-IZ.  Results  of HRGC-MS analysis  of  a:h  sample 80-07-027-43
              for  dichlo-"odibenzof urans.
                                 202
-------
* 251-252   « 253-2;,.
   0,88   8,38   1,19   1,36   2,38   3,19  3,55    4,39  3,13   5,55  6,48
t Q a ,      ,       ,
    ," " '• " ' ' • • ! n ' [ ' • I " I II 1 " I I ' I I II I I I I I I I i in . ri I i i u , ! i n]j , n |, , , i
 re
 58
 48
 38
 26
     1 8 9:; = 1 71 l
    i o e :< = 2 e 4 7
                                               ^J
         Tjm
         28
'""I-"
   48
"I '" ""rrpT
 68    88
rrpnrn
 180
"I""
 120
'"I""'1 rTT1'TT"
  148    160
                                                  ISO    208
  Figure C-14.   Results of HRGC-MS analysis of  ash  sample 80-07-027-43
                 for d^chlorodibenzo-p-dioxins.
                                    203
-------
* 263-278   •  271-272
     19
100
 9C
 8t
 3(
                                   e, 40
    1 8 8 :: « 2 1 S 3
                                i i  I
                                                    8. 29
                                                                   18. 01
   —i—:—i—t—i—i—r—i—i—|—i—r—i—r-
   tea             ise
-i—i—i—]—i—i—i—i—i—i—i—T—i—|—r—i—i—i—n—1~

     200              238
380
Figure C-15.  Results  of HRGC-MS analysis of ash sample 80-07-027-43
              for  trichlorodibenzofurcns.
                                 204
-------
   :35-23S   ft  2C7-289
    3, 19
     1 3 3 -.» 2 ? 1
                    4, 59
  i e
                                   6, <0             3,20           18, 01

                               —I	1	1	', •  I  A I  r .  f  I t  I i  i 1  i I  t 1	1	1
— i — i — i — i — i — i — i — i — i — | — i — i — i — i — -, — i — i — n — i — i — i — i — i — i — i — i — i — i — | — i — i — i — n — i — i

ISO            ISB             260              250
                                                                   308
Figure C-16.  Results of HRGC-MS  analysis  of  ash  sample  80-07-027-43
              for trichlorodibenzo-p-dioxins.
                                205
-------
* 383-384   9 305-306
   6:00     !'18    2'33     3,58    5,18     6.38    7,38    9,18
 « Q Q
   I " " ' ' ' I I I l-lt M I I M ' LLI I I I I t I 1 I I I I 1 I I t I I I I I i i ! I i i I i t i i i i i ,, I i ! i i i i i i i I i i i I i 1 1
     1 0 0 V. = 2 4 4
     1 0 0 \ - 2 3 9
 3i
           53
                  1 I " ' " ' "
                    100
11 "»'<"' I ""
  150    200
'" I » "•i" ' I ••"i "» • I ' ' "•
  250     308     356
Figure C-17.  Results of  HRGC-MS  analysis  of  ash  sample  80-07-027-43
              for tetrachlnrodibenzofurans.
                                206
-------
DS-50 CROS?  SCAN  REPORT, RUN,  ACC4BQ002
» 313-32L  «  T2I-322  0 327-328
   0^00     1:18     2:38     3,53    3,18    6,38     7,38     9,18
I t) 3 | L'_L' I I I 1 1 I I I I I I I I I I I I 1 I • 1 I I 1 I I I ! I I I I I I 1 I , , I . , I , I I | I I ! I , , I , I I I I I I I I I I I I I I I I I I I
     i 111 11 i i i | i i i i i i i i i j i i i i i i i i i [ i i i i i . i i i | i i i i i i i i i [ i i i i i i i rryn
    1        30      108      139     200     253      300      350
 Figure C-18.  Results of HRGC-MS  analysis  of ash sample 80-07-027-43
               for tetrachlorooibenzo-p-dioxins.
                                 207
-------
             a  333-3-40
    0-60   1,13  2,38  3, S3   5=18  6,33   7.58   9,18   10.33 11,53 13,18
 ' 'II I I I I I I II I I I I I • II • I
    11111111111111 i : 11 11111111 11 i [ 11 i 111 i |-| | ii 11 11 i I i j 1111 i; 111 [ 11111 ii 'i.' I 1111111 :1111 1111 i: 11111 ii i 11 i

    1     50     100    150    200   250   300     330   400   450    509
Figure C-19.   Results of HRGC-MS  analysis of ash sample  80-07-027-43
               for pentachlorodibenzofurans.
                                  208
-------
               i'38   3,5S  3.13   6.38  7.38    9,18   10,33 11,58  13,28
  •]i 1111 n mm ii i ii i [ 1111 ii i ii 1111 ii 11 ii [i 'i 1111111 ii 111111111 ri'i i n 11 [i 11111 ii i ] 1111 in 11 [i

  1      59    180    133   208   250   388     356   *'I6   430    560
Figure C-20.   Res-ilts of HRGC-MS  analysis of aoh sample 80-07-0^7-43
               for  pentachlorodibenzo-p-dioxins (resulcs for  the
               ^7Cl4~2,3,7,8-TCOD  internal standard are also  shown
               on lower trace).
                                 209
-------
 100
   °'80      2,17     4.3S     6,55     9,14     11,33     13=52     16,11
  70
   '. i-«»  I  lliuLl^
   •L'^ *''•Yr^^vM//.
  50
  40
  30
                     200       360      488     580
                                                         688
                                                                  788
Figure C-21.   Results of HRGC-MS analysis of ash sample 80-07-027-43
              for hexachlorodibenzofurans.
                                210
-------
 *  389-398  * 391-332
 100
    0, 03      2,17     4,36
  7£
  6k
  3C
  1C
 6,55      9,14     11,33    13,52     16,11

	I I ( I . I I 1 I 1 I I  f I I , II ! I 1 I I I . I I I I I 1 1 '
     188*=223
  2f ^yUv.fV
                                                Vy>V

                           V ^
    I I I I I I I I I [ I I I I I I I I I I I I I I I I I t I I I I 1.1 I I I , I I I I II I I I I I I I I I

    1         100     200       3G0       400     500
                            608      700
Figure C-22.   Results  of HRGC-MS analysis of  ash  sample 80-07-027-43
               for  hexachlorodibenzo-p-dioxins.
                                 211
-------
 * 407-488   t  409-418
   0'00     2-48      5.38      8,28      11,18     14,08

1 0 8 | i ' ' i ' i i i i I i i  ' i i i i i i I . | i i i  i i i i  I i  , i , i , i ,, I , ..... i t .1 1 i i i
                                                                IS, 58
                                                               .I,,,,
     100V.-87
  ee
  50
  18
     V'-i"'jV' "

                        l
      I I I I I I 7 I [ I I I , I I I M I I T I  I I M I I [ I I I I I I I I I I I I

                        288       390       400
                                                     300       639
Figure C-23.   Results of HRGC-MS  analysis of ash sample 80-07-027-43
               for haptaciilorodibenzofurdns.
                                  212
-------
   e.ee    2, js    4,36    6,55   9,15    11.34    13,54   is,13

   i i i i i i i i i I i 11 i i i i i t I i i i i i i i i i 11 i i i i i i i 11 11 i i i i i i i I i i i i t t i i i I i 11 i	11 11 • i i
   '                                     B       I            ij



  5 ipty&£^^
                      HW.V,    ".,        •  ^
                                      OCDF Retention Time
  6(
  5C
  2<
     I I I I IT I 1 | I I I I I I I I I | I I I I I I I I I | I I I 1 I I I I I | I I . I I I I I I ] i i i i i i i i ifi n i ' i • •• I m i



           se      180    _158     290     230     369    338
Figure  C-24.  Results  of HRGC-MS analysis of ash sample 80~07~0?7~-
-------
   0.00      2,40       3,38      8.28      11,19      14.08     16, 58

1 e0 11.1 i > i i i i i L i i i i i i i i i I 1.1 i . . i i i i I i , . . i i 11 j l i . i i i i . i i j_i_i . i i i i i , I 1.1 i.i
    183:: = 211
 80
 50
 •SO
J89
                       203  ,     300
                                                     333
                                                              eee
Figure C-25.  Results of  HRGC-MS analysis of ash sample 80-07-027-43
              for heptachlorodibenzo-p-dioxins (results for the
              37Cl^-l,2.3,4,5,7,8-HpCDD internal standard are
              shown  on  center  trdco)
                                 214
-------
   0.00     2,16    4,36    6,53    9,15    11,34    13,54    11>, 17

    i i I i i i i i i I i i i ' i i i i i I i i i i i i i t i I i i i i u i i i I i i i i i i i i i I i i j i i i j i i I i i i i i i i i i I i i i i
    180^=1581
    180::»1434
 78
 50
  \0
    I i i i i i u i [ i ; i r; in I | ) I I I I I 1 i i ( I I I I i I I i .— '• ' ' ' ' " I ' '• ' • ' ' ' ' ' I ' ' ' ' ' ' ' ' ' I ' ' ' '

   1        59      100      150     20^      250      360      358
Figure C-26.  Results of  HRGC-MS  analysis of ash sample 80-07-02/-43
              for octachlorodibenzo-p-dioxin.
                                 215
-------
BS -50 CROSS  SCAN REPORT, RUN,  VERS6e0Cb

* 256-359  «  319-332  0 327-326
   2. 3f
              3. 58
                        5, 19
                                   £, 38
                                              7, 58
                                                         9, IS
                                                                   1C. 38
 90
 89
 70
 ee
 50
 48
 38
 20
 10
1 1 1 1 1 1 1 1 1 t 1 .
100^=1268
,..,-»«
1 0 9 :•; = 2 e 3 2















/



•
i
^-^-^v— ->

-1 1 1 1 j t f - 1 1 1 '
I 1





1


f 1
I X
1








1


fl

u

1 I 1
ii i i ! i .














,


3
t




\*^ ,. j
LJ

i i 1 1 1













j








•X-
Ij
1
0

"T~T~
1














j

f
I
1
f
n
I
f
i/
i



i I i

1
I
1
1


6
1
1
1





3




Lj-
U
M
u

1 I I
1 It 1






1

j
7




T
•



i
It
, , j
[Mi
M
M
W <


. i i









i 9
i









J.C
r
V/i

v/

I 1 1 1 1
(till)













11







^^
v_
N~— V
Vj


! i i i i t i i t i



TCDD Ti
1. 1.3
2. i.3
3. 1,4
4. 1,3

5. l.J
6. 1,2
12 7, 1,2
•a. 1,2

9. 2,3

10. 1,2


11. 1,3
12. 1,2
i
I
1 *'*—-'•. • •*.
v__

'II 	
                                   2S0
                                              300
                                                         358
                                                                    I
                                                                   480
   Figure C-27.   Lab  A — rnultiple-ion mass chromatogranis  obtained
                  for  12 isomer TCDD standard.
                                 216
-------
* 256-2S9   f  315-322   Qx32?-328
   2, 38
              3,58
                         5,18
                                   6,38
                                               7,58
                                                         9,18
100
                                                                    18, 38
 80
 70
 56
  e-
    1 6 9 * =f 1 1 8 5
    iee--.-=34i
              ''1.'(i I'
                  if
   I I I 1 I I I I I I I I  I I I I I I
100       ISO
                               I I I I I I I I I I I I  I I I I I I I I I I I I I I  1 I I I I I I I I
                                   258         300        330        480
         Figure C-28.   Lab  A — multiple-ion mass  chroir.atograms
                        obtained for 5-isomer TCDD  standard.
                                  217
-------
D.s-50  CROSS sc.-.K REPORT,  Ru*. accissaeas



• 25S-253   * 319-322   0  327-328
              3,58       5,18       6.38        7,38       9,18       18,38
      I ! I  i 1 I I I  I I I I I 1  I I ' I '
                                    259
                                                368
                                                          350        488
                 r ?Q   I ab A 	  multiple ion mass chromatogram
                 O *--' "   l_ '-*1-' ' '          r              nnrt~7nO"7/!O
                        obtained  for  Acurex sample a80-0/-02/-43.
                                   218
-------
T5-S9 CROSS  SCfl-:  REPORT,  RUN: ACCISS0097

* 256-253  «  3 lii--322  0 327-328
   2, 38
10G
                         [ i i i I I i I I  I | I I I I I i I I I [
                                                                   400
          Finure  C-30.   Lab A — multiple ion mass chromatogr^ms
                        obtained for Acurex sample a80-07-027-43.
                                   219
-------
TABLE C-15.  LIST OF CHLOROOIOXIN AND FURAN ISOMER STANDARDS CURRENTLY
             USED AT LABORATORY A
              1-Chiorodibenzo-p-dioxin
              2-Chlorodibenzo-p-dioxin
              2,7-Dichlorodibenzo-p-dioxin
              2,3-Dichlorodibenzo-p-dioxin
              1,2,4-Trich1orodibenzo-p-dioxin
              Tetrachlorodibenzo-p-dioxins — all 22 isomers
                     ,3,7,8-Tetrachlorodibenzo-p-dioxin
                 4-2,3,7,8-Tetrachlorodibenzo-p-dioxin
                 4-2,3,7,8-Tetrachl orodi benzo-p-di oxi n
              1,2,3,7,8-Pentachlorodibenzo-p-diox in
              1,2,4,6,7,9-Hexachlorodibenzo-p-dioxin
              1,2,3,4,7,8-Hexachlorodibenzo-p-dioxin
              1,2,3,4,6,7-Hexachlorodibenzo-p-dioxin
              1,2,3,4,6,7,8-Heptachlorodibenzo-p-dioxin
              3'Cl4-l,2,3,4,6,7,8-Heptachlorodibenzo-p-dioxin
              Detach 1orodibenzo-p-dioxin
              •^Cls-Octachlorodibenzo-p-dioxin
              2,4-Dichlorodibenzofuran
              3,6-Dichlorodibenzofuran
              2,8 Dichlorodibenzofuran
              1,2,4-Trichlorodibenzofuran
              1,2,4,8-Tetrachlorodibenzofuran
              2,3,7,8-Tetrachlorodibenzofuran
              l.,2,4,7,8-Pentachlorodibenzof uran
              1,2,4,6,7,9-Hexachlorodibenzofuran
              1,2,3,4,6,8,9-Heptachlorodibenzofuran
              Octachlorodibenzofuran
                                 220
-------
c•5•1  Samples 07-027-18 (Flyash) anJ 07-027-10 (Bottom Ash)

       These samples were subjected to Soxhlet extraction for 24 hours with
benzene after which the benzene was removed and replaced with petroleum
ether.  The petroleum ether we.s then concentrated to about I ml  and cleaned up
using a Woelm basic alumina column which was first eluted with 10 ml of 2
percent methylene chloride/hexane and the fraction discarded.  The dioxins and
dibenzofurans were then eluted with 50 percent dichloromethane/hexane.  This
eluate was concentrated to 200 yl and submitted for analysis.

C.5.2  Samples 11-043-80 and 10-015-3 (Pond Sludges) and 07-027-03 (ENTA)

       These samples were shaken with JO percent methylene chloride/hexane and
the sorbent placed on the head of a column (30 cm x 18 mm) which had been wet
packed with 40 ml of Fisher A-540 alumina deactivated with 5 percent 1^0 and
topped with 2 gm of ^SO,;.  The column was then eluted with 150 ml of 30
percent methylene chloride in hexane directly into a Kuderna-Danish apparatus
where the column of solvent was reduced to ~20 ml.  This extract was then
subjected to washes with 20 percent KOH, water, concentrated sulfuric ac'id and
again, water.  The extract was then dried over sodium sulfate and concentrated
to about 1 ml prior to Woelm alumina column chromatography as described above.

       The data are presented in Tables C-16 and C-17.  On several of the
samples the recoveries for the monochlorodioxin in the spiked samples are
quite low or nonexistent.  This is due to the washes with concentrated
sulfuric acid.  A cleanup this severe was necessitated since the samples
contained interfering compounds at concentrations many times higher than the
dioxins.  Sulfonation has been found to be an effective way of removing many
of the compounds so it was employed even at the risk cf losing the
monochlorodioxin.  One other concern arising from the use of such severe
cleanup procedures is the possibility of dioxins being formed by the
cyclization of dioxin precursors by any of several possible mechanisms:
         Clx
or the almost quantitative yield of octachlorodibenzodioxin formed directly
from the heating of pentachlorophenol:
                                                      ci
Since these samples were all from various wood treating facilities, it was
expected that they could contain pentachlorophenol and various
ortho-chlorophenols in high concentration relative to any dioxins present.
                                      221
-------
                      TABLE  C-16.   DIOXINS  IN  SAMPLES  -  Ng/g
Sample
07-027-18 (flyash)
07-027-13 Eoike
Spike le'vel
Recovery
Lower detection limit
KCDD
ND
ND
234
-
117
DCDD
ND
51
101
50%
51
T CDD
ND
62
119
C?£
3/C-o
6'J
TCDD
ND
6C
107
56%
54
PCDD
ND
122
223
55%
112
HCDD
ND
237
378
63%
189
H CDD
p
ND
117
217
54%
109
OCDD
ND
312
452
69%
226
07-027-10   (bottom ash)     ND
07-027-10   Replicate     ND
07-027-10   Spike         ND
  Spike level            204
  Recovery
Lower detection limit    102

11-043-80   (pond sludge)P+B  ND
11-043-80   Spike        1142
  Spike level            855
  Recovery               133%
  Solvent blank           ND
Lower detection limit    430
10-015-3   (pond sl.idge)
10-015-3   Replicate
10-015-3   Spike
  Spike level
  Recovery
10-015-3   Spike
  Spike level
  Recovery
Lower detection limit

07-027-03  (Penta)
                     P+A
 ND
 ND
 ND
491

482
983
49%
246
  ND
  ND
  45
  88
 51%
  44

  ND
 325
 370
 88%
  ND
 185

  ND
  ND
 275
 213
129%
 576
 426
135%
 107
 ND
 ND
 65
104
62%
 52

 ND
272
435
63%
 ND
218

 ND
 ND
203
250
81%
496
500
99%
125
                       ND
                       ND
                       71
                       94
                      7 co,
                      / O-&
                       47

                       ND
                      238
                      391
                      61%
                       ND
                      196
 38
148
225
66%
419
450
93%
113
  ND
  ND
 153
 195
 79%
  98

  ND
 558
 816
 68%
  ND
 408

  ND
  ND
 479
 469
102%
 891
 938
 95%
 235
  ND
  ND
 275
 330
 83%
 165

  ND
 959
1381
 69%
  ND
 691

  ND
  ND
 756
 794
 91%
1484
1588
 93%
 397
  ND    298
  ND    381
 198    420
 189    395
104%   105%
  95    158

  ND   2102
 819   259S3
 791   1652
103%      a
  ND     ND
 396    826

 586   2209
 491   2060
 446    666
 455    950
 98%      a
 963   1800
 910   1900
106%    95%
 228    475
                                   1538   17095 >17095
 Recovery not reported  since background OCDD  present  at  levels  greater
 than the spike.
 Probably 1,3,6,8-TCDD.
Interferences too large to allow  quantitation.

ND = None detected below lower  detection limit.
                                      222
-------
                   TABLE C-17.   DIBENZGFURANS IN  SAMPLES - Ng/g
Sample mcno
07-027-18 (flvashN
07-027-18 Replicate
07-027-18 Spike
Spike level
Recovery
Lower detection limit
07-027-10 (Dottom ash)
07-027-10 Replicate
07-02"?-10 Spike
Spike level
Recovery
Lower detection limit
11-043-80 (pond rJudge)
11-&43-80 Spike
Spike level *
Recovery
Solvent blank
Lower detection limit
10-015-3 (pond sludge)
10-015-3 Replicate
10-015-3 Spike
Spike level
Recovery
Solvent blank
Lower detection limit
07-027-03 (Penta)
07-027-03 Replicate
07-027-03 Spike
Spike level
Recovery
ND
29
ND
54
-
27
ND
ND
ND
47
-
24
177a
245
330
74%
ND
165
ND
ND
-
330
-
ND
110
255
105
221
429
51%
di
54
64
49
95
51%
48
ND
ND
60
83
72%
42
a
330
590
56%
ND
295
3f5b
319
441
590
75%
ND
197
ND
3547
2992
762
392%
tri
ND
ND
ND
103
_
52
ND
ND
61
90
67%
45
586
383
640
60%
ND
320
ND
ND
278
640
43%
ND
213
ND
ND
2594
824
215%
tetra
ND
ND
ND
67

34
ND
ND
49
53
84%
29
ND
253
410
62%
ND
205
ND
ND
193
410
47%
ND
137
ND
ND
531
533
99%
penta
ND
ND
HD
154

77
ND
ND
119
135
88%
68
ND
628
950
66%
ND
475
ND
ND
459
950
48%
ND
317
929
905
1061
1233
86%
hexa
ND
ND
ND
263

132
ND
ND
213
229
93%
115
ND
1222
1620
/ J-Q
KD
810
ND
ND
738
1620
40%
ND
540
3088
2289
901
2100
43%
hepta
ND
ND
ND
57
_
29
ND
ND
52
49
106%
25
309
279
350
80%
ND
175
ND
ND
173
350
50%
ND
117
3499
2721
-
452C
c
octa
ND
ND
ND
163

163
ND
ND
127
142
S0%
71
294
628
1010
62%
ND
505
ND
ND
364
1010
36%
ND
337
5471
3850
203
1305
c
••- __
Interferences.
 Isomers other than those used  to spike sample.
CRecovery not given since spike levels were significantly below the level
 present in the sampls,

ND - None detected below lower  detection limit.
                                      223
-------
Th  imtia, cleanup step of chromatographing the samples on a neutral  alumina
column was included to eliminate- the possibility of artifact formation by
removing the possible precursors prior to acid or base washes.

       It was not possible in all :ases to adhere to a strict QA/QC program
due primarily to the inadequate amount of sample received.  Whenever possible,
however, QA/QC Method MCR Method no. 7 was followed without exception.

       The samples were analyzed using MRC Method no. 1 with the exception
that a 1 percent Dexsil 300 column was substituted for the 3 percent Dexsil
400 column.

       In addition, each sample was fortified with 13r -TCDD prior to workup
to serve as an internal standard.                     12

C.6    LABORATORY C ANALYSIS

C.6.1  Extraction and Clean-Up Procedures in Flyash Analyses

       In a recent publication Lustenhouwer, et al., have compared the
efficiency of various solvents to extract PCDDs and PCDFs from flyash and
other participate matter.  The data reported in Table 2, p. 503, clearly shows
that the highest efficiency was found for Soxhlet extraction with toluene on
acid treated material.  In an unpublished study Lab C reported that the
temperature of the solvent in the Soxhlet extractor is also of importance, the
efficiency was found to increase with increasing temp.

       In the Lab C analyses an extraction procedure based on acid treatment
was used followed by Soxhlet extraction with hot tuluene for 36 hrs.  This
should be an optimal procedure for the extraction of PCDDs and PCDFs.

       The extraction procedure was followed by a clean-up on an alumina
column resulting in a fraction where PCDDs and PCDFs could be determined
without interferring artifacts.

C.6.2  Separation, Quantification and Confirmation

       In the Lab C analyses a 55 m Silar 10 c glass capillary column was used
for the separation of the PCDDs and PCDFs.  The lab recently reported using
column to separate 2,3,7,8-tetra-CDD from all other 21 TCDD isomers, thus
allowing an unambigous identification of the highly toxic 2,3,7,8-isomer.

       The quantification is based on mass fragmentography and comparison with
calibration curves of kncwn amounts of 2,3,7,8-tetra-CDD, 1,2,3,7,8-hexa-CDD
and octa-CDD, 2,3,7,3-tetra-CDF, 1,2,3,4,7,8,-hexa-CDF and octa CDF-

       Positive identification of PCDD and PCDF isomers was based on the
following requirements:

       a)  Identical retention times with synthetic standards on one (or two)
           glass capillary columns.
                                      224
-------
        t>)   Complete mass-spectra showing the expected  chlorine-clusters  for
            the parent ions and the expected fragmentation.

 _       The mass fragnento grams of the plant C ash  sample  80-07-027-18  is  given
 in  Figures C-31 and 32.   A study of these figures  reveals:

        a)   All  the major peaks co-elute  with synthetic  standards.

        b)   The  possibility of analyzing  false positives  is  very very small,
            p  <  lO-iO.

        c)   The  same pattern of PCDDs  is  observed as  in  other  "normal"  flyash
            samples, see  Figure C-33.   This  indicates the  same  precursors,
            namely chlorophenols.

        d)   2,3,7,8,-tetra-CDD is  a very  very minor peak.

        e)   >  90i  of the  PCDDs are lower  chlorinated  congeners  than  octa-CDD.

        f    A  difference  in the pattern of PCDFs  is observed compared to  other
            "normal" flyash samples, see  Figure C-34.

        In  the  analytical  system  used  by  Lab A a  peak from the  ash extract  is
 apparently co-eluting with the authentic 2,3,7,8-TCDD standard.

        Lab C  personnel believe they can  unambiguously separate the
 2,3,7,8-isomer  from the  other 21  isomers.   Consequently they have already
 performed  a deeper  study of possible  thermal  isomerization  of  2,3,7,8-TCDD.

        Lab  C  analyses are in  disagreement with the Lab A  analyses.  Figure
 C-32 clearly  shows  that  2,3,7,8-TCDD  is  not present  in these ash samples.

 C.fa.3   The  Pattern  of PCDDs

        The  same pattern  of PCDD  is  observed in Lab C data as in other European
 flyash  samples, see Figure C-33.   Chlorinated  phenols are the precursors to
 the PCDDs  found in  all these  samples.  Lab  C  has also observed that more than
 90i of  the  PCDDs  are lower chlorinated more than the expected OCDD.  This is
 due to  a nonspecific dechlorination of OCDD previously studied by Rappe et al.

 C.6.4  The  Pattern  of PCDFs

       The  pattern  of PCDFs observed  is  slightly different  than that found in
 "normal" flyasii analyses  indicating different precursors.   In the normal  fly
 ash PCBs are the major precursors,  in  the Acurex samples the precursors are
believed to be  impurities  in  the  commercial Penta,  Figure C-34.

       Standard isomers  for PCDF's  and PCDD's used by Laboratory C  included at
 least one  isomer for each  monomer  and  included 100 individual  isomers.
                                      225
-------
                           IMk»

                       nM^'l n  •
                    iuii —j  M \':**
                     i   Ii *i V>. l' .  :
                                  t)*l
                                 nn
                                mi
                            "•»
            »so'
Fiaure  C-31   Laboratory C mass fragmentogram of tetra-,  penta-
  y •        '   hexa-  and hepta-CDDS from a flyash sample.
                                226
-------
                           N
                           • 'U
ill
                   •?"«o*      i-jo"
                                              J'C^      ^oo"
Figure C-32.   Laboratory C mass fragnentogram of tetra-, penta-

               hexa- and hepta-CDFS from  a  flyash sample.
                               227
-------
Typical
European
Ash
       1
                    /sJLJl	
                                                          r^/f .TO a
   Plant C
   Ash
           ai*-*"
       AUIIt  ,

       JU
                       II Hit

                   .>;j ul
                   *^—• •
                      Bit'«
                                  BUI |
                                O1'«|
n>/e yes
                                                              *•»/• J3
          Figure  C-33.   Comparison of PCDD in Plant C ash and typical
                         European  incinerator ash.
                                      228
-------
       European
       Ash
Plant C
Ash
_A
                              OUTI

                              1 HKIt
                                                                      -/. 37?
                      J
A _A^-
J
— 	 i 	 . 1... 	 — 	 _,.,i 	 _,..--!
DU
i
if I'll1* »"
ftir 	



                                     »3
-------